CN103814062A

CN103814062A - Sulfonic acid group-containing polymer, sulfonic acid group-containing aromatic compound and method of making same, as well as polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell using same

Info

Publication number: CN103814062A
Application number: CN201280045389.0A
Authority: CN
Inventors: 陈桥; 邵芳可; 吴刚; 出原大辅; 梅田浩明
Original assignee: Toray Advanced Materials Research Laboratories China Co Ltd
Current assignee: Toray Industries Inc
Priority date: 2011-09-20
Filing date: 2012-09-06
Publication date: 2014-05-21
Anticipated expiration: 2032-09-06
Also published as: CN103814062B; JP5845762B2; JP2013064080A

Abstract

It is an object of the present invention to provide a sulfonic acid group- containing polymer and a sulfonic acid group-containing aromatic compound, which have excellent proton conductivity even under the low humidification condition, are excellent in mechanical strength and chemical stability and, moreover, can attain high output and excellent physical durability when processed into a solid polymer fuel cell, as well as a polymer electrolyte material, a polymer electrolyte molded product and a solid polymer fuel cell respectively using the same. The sulfonic acid group-containing polymer of the present invention is a sulfonic acid group-containing polymer comprising a constituent unit containing a sulfonic acid group (A1), and a constituent unit not containing a sulfonic acid group (A2), wherein the polymer contains a constituent unit having a specified structure as at least one constituent unit containing a sulfonic acid group (A1) at 25 mol% or more based on a sum of the constituent unit containing a sulfonic acid group (A1). Further, the polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell of the present invention are constituted using such a sulfonic acid group-containing polymer.

Description

Containing sulfonic group polymkeric substance, containing sulfonic aromatics and preparation method thereof, polymer electrolyte, polymer dielectric molding and solid polymer type fuel battery

Technical field

The present invention relates to a kind of containing sulfonic group polymkeric substance, containing sulfonic aromatics and preparation method thereof, particularly a kind of practical polymer electrolyte, even if still there is under low moisture conditions good proton conductivity, and can obtain good mechanical property, chemical stability and physical durability; And polymer dielectric molding and solid polymer type fuel battery.

Background technology

Fuel cell is a kind of electric organ, is for example, by electrochemical oxidation fuel: hydrogen or methyl alcohol, thus produce electric energy, because belonging to clean energy, it extremely gazes in recent years.Particularly there is lower standard processing temperature and the high-energy-density of approximately 100 ℃ due to solid polymer type fuel battery; so expection can be widely used on a small scale or decentralized electric power produces facility; or packaged type main body, as the electric organ of automobile or ship.Fuel cell also enjoys and gazes at because can be used as the power supply of small type mobile devices or handheld device, and expects to be applied to mobile phone, Personal Computer etc. to replace the store batteries such as nickel metal hydride, lithium ion battery.

In fuel cell, conventionally using meeting there is to produce the anode of reaction of electric power and negative electrode and between anode and negative electrode as the polymer electrolyte film composition membrane-electrode assemblies (below sometimes referred to as MEA) of proton conductor, form battery unit with this MEA of barrier film double team again, then form fuel cell by battery unit.Electrostrictive polymer very thin films is mainly made up of polymer electrolyte.Polymer electrolyte also can be used for the tackiness agent of electrode catalyst layer etc.As polymer electrolyte film, first it must have high proton conductivity, even and if under high temperature low humidity condition, polymer electrolyte film still must have high proton conductivity.Polymer electrolyte film also needs to have barriers function, prevents the direct reaction between fuel and oxygen, so electrolytic thin-membrane will have low fuel perviousness.In addition, electrolytic thin-membrane also needs to have the chemical stability that can bear strong well-oxygenated environment during operation of fuel cells, can bear film thinning and reexpansion and dry and maintenance physical strength and physical durability etc.

The polymer electrolyte film " Nafion " (registered trademark) (Du Pont company product) being widely used is perfluorinated sulfonic acid polymer.Because Nafion (registered trademark) is through synthetic manufacture of multistage, so Nafion exists the problems such as expensive and fuel permeability is high.In addition, film is owing to expanding and dry losing physical strength and physical durability, cannot also be noted in problems such as applied at elevated temperature, aftertreatment and material regeneration difficulties because softening temperature is low.

Therefore, develop energetically in recent years hydro carbons electrolytic thin-membrane as polymer electrolyte film, it can replace Nafion (registered trademark), and price is not expensive, and the excellent property of film.

For example existing a kind of segmented copolymer, it has does not introduce sulfonic hydrophobic chain segment and introduces sulfonic hydrophilic segment, hydrophobic chain segment is polyethersulfone (PES) or polyetherketone, and hydrophilic segment is for containing sulfonated polyether sulfone or sulfonated polyether ketone (patent documentation 1～2).In above-mentioned document, as hydrophilic segment, used all phenyl 50% in introduce and have sulfonic component units, that is, in a kind of 2 phenyl, introduce the alternating copolymer that has in 2 sulfonic aromatic series dihalide and 2 phenyl introducing have sulfonic bis-phenol.Conventionally because these PES and polyetherketone are to use electrophilic aromatic series dihalide and supplied for electronic bis-phenol aromatic series to carry out nucleophilic substitution to react and synthesize, so the sulfonic introducing of electrophilic is limited to aromatic series dihalide one side, be difficult to sulfonic group to introduce the more than 50% of all phenyl.Therefore, present inventor thinks, in the prior art, further improves sulfonic local density and the proton conductivity that improves under low humidity condition is limited in hydrophilic segment.

Patent documentation 3 reported a kind of synthetic comprise be respectively 50,30 and 20 % by mole 4, the mixture of two sulfonated products, three sulfonated products and four sulfonated products of 4 '-difluorodiphenyl base ketone, by the method for this mixture and bisphenol fluorene copolymerization.Owing to being 20 % by mole containing the content of four sulfonated products in sulfonic component units, therefore the improvement degree of the proton conductivity under low humidity condition is restricted.In the document, four sulfonated products can not optionally be synthesized, and these two sulfonated products, three sulfonated products and four sulfonated products have similar polarity conventionally, even so use chromatographic techniques etc. are still difficult to be isolated and purifying, in addition, the molar content of four sulfonated products cannot increase.

The one of having reported non-patent literature 1 contain polyethersulfone (PES) as hydrophobic chain segment, using sulfonic group introduce all phenyl 100% in sulfonated polyether sulfone as the segmented copolymer of hydrophilic segment.Present inventor confirms, in the document, after the identical polymkeric substance obtaining with patent documentation 1, sulfonic group introduced in the phenyl with high electron density of ether, and like this, due to reversible reaction, desulfonation reacts and is easy to carry out.In addition, the present invention thinks, also has the problem of chemical stability deficiency, and, sulfonation reaction and redeposition after needing, therefore, number of reaction stages can increase, and makes cost increase.

Similarly, the polymer electrolyte obtaining by prior art is not enough to, as the means of improving economy, processibility, proton conductivity, physical strength, chemical stability and physical durability, cannot become polymer electrolyte useful in industry.

(prior art document)

(patent documentation)

Patent documentation 1: No. 2009-235158th, TOHKEMY

Patent documentation 2:WO08/018487

Patent documentation 3: No. 2007-84739th, TOHKEMY

(non-patent literature)

Non-patent literature 1:Journal ofPolymer Science A Polymer Chemistry, 48,2757,2010

Summary of the invention

(technical problem to be solved)

Consider the above-mentioned condition of prior art, one of object of the present invention is for providing a kind of containing sulfonic group polymkeric substance and containing sulfonic aromatics, even if still there is under low moisture conditions good proton conductivity, physical strength and chemical stability, in the time being processed into solid polymer type fuel battery, can obtain high output and good physical durability; In addition, the invention provides and contain sulfonic group polymkeric substance and the preparation method containing sulfonic aromatics, and use the polymer electrolyte, polymer dielectric molding and the solid polymer type fuel battery that contain sulfonic group polymkeric substance and contain sulfonic aromatics.

(technical scheme of dealing with problems)

In order to address the above problem, the present invention adopts following means.A kind of containing sulfonic group polymkeric substance, it comprises: contain sulfonic component units (A1) and do not contain sulfonic component units (A2), wherein, containing containing the identical or different component units of counting 25 % by mole or above one or more and have formula (S1) structure by its integral molar quantity in sulfonic component units (A1):

(Chemical formula 1)

Having in the component units of formula (S1) structure, each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) _2-in one; Each Z ¹be O or S independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; * be and there is the part of formula (S1) or the site that other component units is combined.

Of the present invention have the structure of following formula (M1) containing sulfonic aromatics, and the content with the aromatics of following formula (M2) structure is 5 % by weight or following.In addition, the present invention also provides the polymer electrolyte, polymer dielectric organizer and the solid polymer type fuel battery that use above-mentioned block polymer.

(Chemical formula 2)

In formula (M1) and (M2), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; Each Y ¹be at least one in F, Cl, Br and I independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; M be 0 or 1, n be 0 or 1.

(effect of invention)

According to the present invention, can provide a kind of containing sulfonic group polymkeric substance and containing sulfonic aromatics, even under low moisture conditions, still there is good proton conductivity, physical strength and chemical stability can obtain high output and good physical durability in the time being processed into solid polymer type fuel battery; In addition, the present invention also provides containing sulfonic group polymkeric substance and containing the preparation method of sulfonic aromatics, and uses containing sulfonic group polymkeric substance and containing polymer electrolyte, polymer dielectric molding and the solid polymer type fuel battery of sulfonic aromatics.

Accompanying drawing explanation

Fig. 1 illustrates the looks of phase separation structure.

Fig. 2 is the reaction product of embodiment 17 ¹h-NMR spectrogram.

Fig. 3 is the reaction product of embodiment 22 ¹h-NMR spectrogram.

Fig. 4 is the reaction product of embodiment 25 ¹h-NMR spectrogram.

Fig. 5 is the reaction product of comparative example 7 ¹h-NMR spectrogram.

Fig. 6 is the reaction product of comparative example 8 ¹h-NMR spectrogram.

working of an invention mode

The present invention will be described in more detail below.

In order to overcome the problems referred to above, present inventor conducts in-depth research, found that, introduce and have 4 sulfonic specific composition unit by using in 2 phenyl ring, can increase partly containing sulfonic group polymkeric substance and containing the sulfonic group density of the formed proton conduction passage of sulfonic aromatics, bring into play under low moisture conditions excellent proton-conducting and electric power generation property, the processibilities such as excellent film forming, good oxidation-resistance, the chemical stability such as Green Tea Extract or resistance to hydrolysis as, film physical strength, and the premium propertiess such as physical durability such as heat resistanceheat resistant water-based, during especially as electrolyte fuel cells film, can solve as above problem simultaneously, and complete on this basis the present invention.

; the invention provides a kind of containing sulfonic group polymkeric substance; it comprises: contain sulfonic component units (A1) and containing sulfonic component units (A2), wherein: containing containing the identical or different component units of counting 25 % by mole or above one or more and have formula (S1) structure by its integral molar quantity in sulfonic component units (A1):

(chemical formula 3)

Having in the component units of formula (S1) structure, each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; Each Z ¹be O or S independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; * be and there is the part of formula (S1) or the site that other component units is combined.

In the present invention, component units is defined as and in main chain, is inserted with Z ¹the component units of (O or S), as there is the component units of formula (S1).

Of the present invention have containing sulfonic component units (A1) and not containing sulfonic component units (A2) containing sulfonic group polymkeric substance.Of the present invention can have containing sulfonic group polymkeric substance multiple different from sulfonic component units (A1).This polymkeric substance also can have multiple different not containing sulfonic component units (A2).

The sulfonic group polymkeric substance that contains of the present invention can form proton conduction passage, and because it contains by counting 25 % by mole or the above component units with formula (S1) containing the integral molar quantity of sulfonic component units (A1) as containing sulfonic component units (A1), thereby, proton-conducting under low humidity condition increases, and sulfonic group density exceedes previously containing 2 sulfonic component units.

The angle of the proton-conducting from low humidity condition is considered, the component units with formula (S1) is better more greatly by the molar ratio (%) of the integral molar quantity containing sulfonic component units (A1), and must be 25 % by mole or more than, be preferably 50 % by mole or more than, more preferably 75 % by mole or more than, and most preferably 95 % by mole or more than.In the time that the molar ratio of component units with formula (S1) is less than 25 % by mole, sometimes have the situation of the proton-conducting deficiency under low humidity condition, be therefore not suitable for.

In the present invention, M ¹example comprise any metallic cation, ammonium cation NR ⁴⁺(R is organic radical) etc.Metallic cation can use without specific limited in the situation that its valence mumber etc.Preferred metallic cation comprises Li, Na, K, Cs, Rh, Mg, Ca, Sr, Ti, Al, Fe, Pt, Rh, Ru, Ir, Pd etc.Wherein, more preferably of the present invention containing using in sulfonic group polymkeric substance not expensive and easily replacing Na, K, Cs or the Li of proton.R is preferably the alkyl of 1～10 carbon atom.

In the present invention, consider chemical stability and cost, X ¹more preferably ketone group (CO-), sulfuryl (SO ₂-) or direct key, more preferably ketone group or sulfuryl, consider physical durability, most preferably is ketone group.Consider cost and physical durability, Z ¹for O or S, most preferably be O.Most preferably, X ¹for ketone group and Z ¹for O.

There is the component units of formula (S1) because of its contained X ¹base and sulfonic electrophilic effect and there is good chemical stability and the high proton power of dissociating, in addition, forming containing sulfonic group polymkeric substance, particularly when segmented copolymer, can increase partly sulfonic group density, therefore form proton conduction passage, even if still can realize under low moisture conditions good proton-conducting.

The component units preferably with formula (S1) comprises the have following formula component units of (S1～1) to (S1～114).The invention is not restricted to these.Consider manufacturing cost and physical durability, more preferably there is the component units of following formula (S1～1), (S1～2), (S1～5) and (S1～9) to (S1～11), more preferably there is again the component units of following formula (S1～1), (S1～2) and (S1～5), most preferably be the there is following formula component units of (S1～1).In the present invention, preferably use multiple above-mentioned component units.In some cases, according to the substituting group of sulphonating agent kind and starting compound and the position of p-sulfonic acid base is done further to change, the also different component units in preferred sulfonic group introducing position.

(chemical formula 4)

(chemical formula 5)

In formula (S1～1) in (S1～14), M ¹for hydrogen, metallic cation, ammonium cation or there is the alkyl of 1～20 carbon atom.

The following describes of the present invention containing sulfonic group polymkeric substance.

In the present invention, for containing the kind of sulfonic group polymkeric substance without special restriction.

Its object lesson comprises containing sulfonic aromatic polyether class, as contained sulfonic aromatic polyether ketone, contain sulfonic aromatic polyether sulfone or containing sulfonic aromatic polyether phosphine oxide; Contain sulfonic aromatic series polysulphide, as vulcanized ketone containing sulfonic fragrant adoption, vulcanizing sulfone or contain sulfonic fragrant adoption sulfidation-oxidation phosphine etc. containing sulfonic fragrant adoption.

In the present invention, the preferred above-mentioned repeating structure that contains sulfonic aromatic polyether class and there are one or more identical or different formulas (S2) containing sulfonic aromatic series polysulphide:

(chemical formula 6)

Having in the repeating structure of formula (S2), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; And each Z ¹be O or S independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; Ar ¹for the divalent radical containing aromatic ring.* be and there is the part of formula (S2) or the site that other repeating structure is combined.

In the present invention, this repeating structure comprises one or more component units, be repeatedly present in polymkeric substance, and these component units might not be adjacent to repeat exist, another kind of component units can be present between this repeating structure.Or this repeating structure can exist together with kind of repeating structure, and another kind of repeating structure can be present between this repeating structure.

Consider chemical stability and cost, X ¹more preferably ketone group (CO-), sulfuryl (SO ₂) or direct key, more preferably ketone group or sulfuryl, consider physical durability, most preferably is ketone group.Consider cost and physical durability, Z ¹for O or S, and most preferably be O.Most preferably, X ¹for ketone group and Z ¹for O.

Consider cost and chemical stability, preferably, containing sulfonic aromatic polyether ketone or containing sulfonic aromatic polyether sulfone, most preferably be containing sulfonic aromatic polyether ketone.

These can be by having being reacted and synthesized by aromatic series nucleophilic substitution with any dihydric phenol aromatics containing sulfonic aromatics (dihalide compound) of following formula (M1) containing sulfonic aromatic polyether.Dihydric phenol compound is not particularly limited, can considers chemical stability, physical durability, cost etc. and suitably selection.Introducing has sulfonic dihydric phenol compound also can under the prerequisite of scope that does not affect effect of the present invention, be used as monomer, but considers reactivity, more preferably not containing sulfonic dihydric phenol compound.

(chemical formula 7)

Having in the compound of formula (M1), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; Each Y ¹be at least one in F, Cl, Br or I independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently.

For containing sulfonic aromatics, consider chemical stability and manufacturing cost, further preferably there is the sulfonic aromatics that contains of following formula (M1～2) or (M1～3), most preferably there is the sulfonic aromatics that contains of following formula (M1～3).Conventionally, because these are synthetic by the sulfonation reaction of aromatics containing sulfonic aromatics, so sulfonic group is introduced to ortho position or the electrophilic base X of halogen atom ¹between position, but having formula (S1～9) to the component units of (S1～14), this position is not limited to the ortho position of halogen atom, sulfonation position can be selected by selecting suitable sulphonating agent and functional group.

(chemical formula 8)

Having in the compound of formula (M1～2) or (M1～3), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; Each Y ¹be at least one in F, Cl, Br or I independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently.

At this, Y ¹can comprise fluorine, chlorine, bromine and iodine, but consider reactivity, preferably fluorine and chlorine, most preferably fluorine.Electrophilic base X ¹comprise ketone group, sulfuryl, direct key ,-PO (R ¹)-(wherein R1 be organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) _2-.Consider chemical stability and cost, preferably ketone group (CO-), sulfuryl (SO _2-) or direct key, further preferred ketone group or sulfuryl, consider physical durability, most preferably ketone group.Most preferably, X ¹for ketone group and Y ¹for F.

Because aromatic sulfonic acid derivative of the present invention is due to X ¹the electrophilic effect of group and there is good chemical stability, and then, in the time being formed as containing sulfonic group polymkeric substance, can increase partly sulfonic group density, realize its good proton-conducting under low moisture conditions.

By suitably selecting content molar ratio of chemical structure, aromatic sulfonic acid derivative of the present invention etc., can control various character, as processibility, (structure) territory size, degree of crystallinity/amorphous degree, physical strength, proton conductivity and dimensional stability.

In the present invention, the Ar in formula (S2) ¹for comprising the divalent radical of aromatic ring, be not particularly limited.Consider chemical stability and physical durability, preferably there is following formula (q1) or divalent radical (q2) as Ar ¹.Further preferably there is the divalent radical of following formula (q1).Consider chemical stability and cost, X ²base is preferably ketone group (CO-), sulfuryl (SO ₂) or direct key, more preferably ketone group or sulfuryl, consider physical durability, most preferably is ketone group.

Consider chemical stability and manufacturing cost, formula (S2) more preferably has the repeating unit of following formula (S2-1): (chemical formula 9)

Having in the repeating structure of formula (S2-1), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; Each Z ¹be O or S independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently.Ar ¹for thering is following formula (q1) or divalent radical (q2).X ¹, Z ¹, Ar ¹, and M ¹can be two or more different groups.* be and there is the part of formula (S2) or the site that other repeating structure is combined.

(Chemical formula 1 0)

In formula (q1), X ²for ketone group, sulfuryl, direct key ,-PO (R ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one.There is formula (q1) or group (q2) and can be included sulfonic group in interior any group replacement.

Consider chemical stability and cost, X ¹be preferably ketone group (CO-), sulfuryl (SO ₂) or direct key, more preferably ketone group or sulfuryl, consider physical durability, most preferably is ketone group.Consider cost and physical durability, Z ¹for O or S, most preferably be O.Most preferably, X ¹for ketone group and Z ¹for O.The repeating structure with formula (S2) most preferably is the have following formula repeating structure of (S3):

(Chemical formula 1 1)

In formula (S3), each M ¹it is independently the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom.* be and there is the part of formula (S3) or the site that other repeating structure is combined.

Having especially preferred object lesson in the repeating structure of following formula (S2) is, the X in formula (q1) ²for ketone group (CO-), sulfuryl (SO ₂) or the direct structure of key, and there is the unit structure of formula (q2) can be by thering is synthesizing containing sulfonic aromatics (dihalide compound) and the nucleophilic substitution reaction that has between the aromatic series of dihydric phenol compound of following formula (Y-1) to (Y-4) of formula (M2).Divalent sulfur alkylol cpd (the heteroatoms derivative of dihydric phenol compound)

Also be preferred example.

(Chemical formula 1 2)

Consider the cationoid reaction of low cloud density and inhibition and hydroxyl radical free radical in phenyl ring, preferably there is the dihydric phenol compound of formula (Y-1) to (Y-2), consider most preferably there is the dihydric phenol compound of formula (Y-1) from the angle of water tolerance and degree of crystallinity.

For the dihydric phenol compound containing sulfonic group polymkeric substance of the present invention, be not particularly limited, can in the situation that considering chemical stability, physical durability, cost etc., carry out aptly copolymerization.Introducing has sulfonic dihydric phenol compound also can effect of the present invention not being had to negative impact, does not reduce on reactive scope of hydroxyl and position as monomer, but considers reactivity, more preferably containing sulfonic dihydric phenol compound.The object lesson of other dihydric phenol is for having the dihydric phenol compound of following formula (Y-5) to (Y-30) structure:

(Chemical formula 1 3)

The dihydric phenol compound with formula (Y-5) to (Y-7) can be substituted arbitrarily.

(Chemical formula 1 4)

The dihydric phenol compound with formula (Y-8) to (Y-11) can be substituted arbitrarily, and n is more than or equal to 1 integer.

(Chemical formula 1 5)

The dihydric phenol compound with formula (Y-12) to (Y-19) can be substituted arbitrarily, and n and m are respectively the integer that is more than or equal to 1, and Rp is organic group.

(Chemical formula 1 6)

The dihydric phenol compound with formula (Y-20) to (Y-30) can be substituted arbitrarily.

In the present invention, in order to obtain the there is formula repeating structure of (S3), preferably in dihydric phenol compound, introduce protecting group, and after polymerization or being shaped, compound is gone to protection and transform into the there is formula repeating structure of (S3).Consider reactive behavior and chemical stability, the dihydric phenol compound with protecting group be preferably there is following formula (r1) to the compound of (r10) or derived from the derivative of these dihydric phenol compounds.

(Chemical formula 1 7)

Consider chemical stability, in these dihydric phenol compounds, more preferably there is the compound of formula (r4) to (r10), further preferably there is formula (r4), (r5) or compound (r9), most preferably there is the compound of formula (r4).

In the present invention, not affecting in the scope of effect of the present invention, maintaining under the prerequisite of the proton conductivity under low humidity condition, can by formula (M1) and (M2) in addition containing the active dihalide compound of sulfonic aromatic series for copolymerization.There is sulfonic monomer preferably but be not limited to 3,3 '-disulfonic acid-4,4 '-dichloro diphenylsulfone, 3,3 '-disulfonic acid-4,4 '-difluorodiphenyl base sulfone, 3,3 '-disulfonic acid-4,4 '-dichloro diphenylketone, 3,3 '-disulfonic acid-4,4 '-difluorodiphenyl base ketone, 3,3 '-disulfonic acid-4,4 '-dichloro diphenyl benzene phosphine oxide or 3,3 '-disulfonic acid-4,4 '-difluorodiphenyl base benzene phosphine oxide etc.

In the active dihalide compound of aromatic series, there is sulfonic compound and do not there is sulfonic compound copolymerization, or thering is the compound copolymerization of different sulfonic group introduction volumes, therefore sulfonic group density is controlled.But, of the present invention is segmented copolymer containing sulfonic group polymkeric substance, consider from the angle of guaranteeing the proton-conducting continuity and the improvement low humidity condition in proton conduction path, more preferably the active dihalide compound of aromatic series that does not have the active dihalide compound of sulfonic aromatic series or have a kullgren acid base introduction volume is not carried out to copolymerization.

The preferred example without the active dihalide compound of sulfonic aromatic series comprises: 4,4 '-dichloro diphenylsulfone, 4,4 '-difluorodiphenyl base sulfone, 4,4 '-dichloro diphenylketone, 4,4 '-difluorodiphenyl base ketone, 4,4 '-dichloro diphenyl benzene phosphine oxide, 4,4 '-difluorodiphenyl base benzene phosphine oxide, 2,6-dichlorobenzonitrile or 2,6-difluorobenzonitrile etc.Consider from the angle that improves degree of crystallinity, physical strength, physical durability and hot water resistance, wherein further preferably 4,4 '-dichloro diphenylketone or 4,4 '-difluorodiphenyl base ketone, considers polymerization activity, most preferably is 4,4 '-difluorodiphenyl base ketone.The active dihalide compound of these aromatic series can be used alone, also the active dihalide compound of the multiple aromatic series of use capable of being combined.

Halogenated aromatic oxy-compound is not particularly limited, and its example comprises 4-hydroxyl-4 '-chlorodiphenyl base ketone, 4-hydroxyl-4 '-fluorine diphenylketone, 4-hydroxyl-4 '-dichloro diphenylsulfone, 4-hydroxyl-4 '-fluorine sulfobenzide, 4-(4 '-Hydroxybiphenyl) (4-chloro-phenyl-) sulfone, 4-(4 '-Hydroxybiphenyl) (4-fluorophenyl) sulfone, 4-(4 '-Hydroxybiphenyl) (4-chloro-phenyl-) ketone or 4-(4 '-Hydroxybiphenyl) (4-fluorophenyl) ketone etc.These compounds can use separately, also can use with the form of the mixture of two kinds or above compound.In addition, these halogenated aromatic oxy-compound also can be in the reacting of activation dihalide aromatics and aromatic dihydroxy compound one react, synthetic aroma adoption ether compound.

Consider the proton conductivity forming under proton conduction passage and low humidity condition, more preferably of the present invention one or more containing sulfonic segment (B1) and one or more not containing the segmented copolymer of sulfonic segment (B2) for containing containing sulfonic group polymkeric substance, segment (B1) and segment (B2) all contain the component units with formula (S1).In the time that the component units content with formula (S1) is less than 25 % by mole, not enough sometimes as the proton-conducting under the low humidity condition of effect of the present invention, be therefore not suitable for.

In the present invention, above-mentioned segment is the part-structure in segmented copolymer, and the combination that it comprises a kind of repeating structure or multiple repeating structure has 2000 or above molecular weight.

In the present invention, be to comprise the segment with sulfonic repeating structure containing sulfonic segment (B1), and comprise one or more sulfonic repeating structure.This can repeat to be present in segment containing sulfonic repeating structure, but not necessarily will be adjacent to repeat exists, and another kind of component units can be present between this repeating structure.Or this repeating structure can exist together with multiple repeating structures, and another repeating structure can be present between multiple repeating structures.

In the present invention, be not to comprise the not segment containing sulfonic repeating structure containing sulfonic segment (B2), and comprise not containing one or more sulfonic repeating structures.This can not repeat to be present in segment containing sulfonic repeating structure, but not necessarily will be adjacent to repeat exists, and another component units can be present between this repeating structure.Or this repeating structure can exist together with multiple repeating structures, and another repeating structure can be present between multiple repeating structures.

In the present invention, above-mentioned segment is called " not containing sulfonic segment ", but segment (B2) can contain a small amount of sulfonic group under the prerequisite that does not affect effect of the present invention.Below, " not containing sulfonic group " uses with identical meanings sometimes.

The segmented copolymer being obtained by the present invention is that two or more mutual incompatible section of chain contained to sulfonic hydrophilic segment and be not connected to form a polymer chain containing sulfonic non-hydrophilic segment.In this segmented copolymer, due to the short range interaction being produced by the mutual exclusion between chemically not identical section chain, this segmented copolymer can be separated, form nanometer territory or micron territory containing each segment chain, and the effect of the Long range interaction producing due to the mutual covalent linkage of segment chain, each territory is arranged by order in accordance with regulations.The high-sequential structure forming by the territory aggegation that comprises each segment chain is called nanometer or micron phase separation structure, and for the ionic conduction in polymer electrolyte film, the spatial disposition of film intermediate ion conduction segment is extremely important.At this, territory (domain) is illustrated in similar segment aggegation in one or more polymer chain and the agglomerate that produces.

Because of containing containing the there is formula component units of (S1) in sulfonic segment (B1) as chemical structure, the segmented copolymer being obtained by the present invention can improve by forming part the proton conduction passage of sulfonic group density and realize chemical durability or physical durability and good proton-conducting, still has especially under low moisture conditions high proton conductivity.

Suitably select the chemical structure, section chain length, molecular weight, loading capacity of the segmented copolymer being obtained by the present invention etc., can control the various character of polymer electrode material, as processibility, (structure) territory size (domain size), degree of crystallinity/amorphous degree, physical strength, proton-conducting and dimensional stability.

By with containing sulfonic segment (B1) formative region, the segmented copolymer that the present invention obtains is in the time being formed as polymer electrode material or electrostrictive polymer very thin films, even still can realize under low moisture conditions good proton-conducting.

Next explanation is containing sulfonic segment (B1).

Be characterized as it containing sulfonic segment (B1) and contain the there is formula component units of (S1), preferably chemically stable, because sucting electronic effect has peracidity and highdensity sulfonic group is introduced to segment wherein, like this, can obtain the good segmented copolymer of proton-conducting under low moisture conditions.

Similarly consider the proton-conducting under low humidity condition, as the polymkeric substance of the preferred object lesson containing sulfonic group polymkeric substance of the present invention, also preferred as containing sulfonic segment (B1) as the polymkeric substance of its especially preferred example.As mentioned above, its example comprises the have formula repeating structure of (S2-1), is preferably the have formula repeating structure of (S2), and more preferably has the repeating structure of formula (S3).

Next illustrate not containing sulfonic segment (B2).

As not containing sulfonic segment (B2), preferably chemically stablize and because strong intermolecular cohesive force shows crystalline component units, like this, can obtain the segmented copolymer that physical strength, dimensional stability and physical durability are good.

More preferably it does not have the repeating structure of following formula (P1) to the segmented copolymer being obtained by the present invention containing sulfonic segment (B2):

(Chemical formula 1 8)

The site with formula (P1) can be substituted arbitrarily, but not containing sulfonic group.Y ³for electrophilic group, Z ³for electrophilic group, O or S.* be and there is the part of formula (P1) or the site that other component units is combined.

At this, electrophilic group Y ³comprise-CO-of object lesson ,-(CF ₂) _n-(integer that wherein n is 1～5) ,-C (CF ₃) ₂-,-SO ₂-,-PO (R ¹)-(be R wherein ¹for organic radical) etc.Consider chemical stability and cost, wherein more preferably-CO-and-SO ₂-, consider physical durability, most preferably be-CO-.

Z ³object lesson comprise electrophilic base, as-CO-,-(CF ₂) _n-(wherein n is 1 to 5 integer) ,-C (CF ₃) ₂-,-SO ₂-, with-PO (R ¹)-(be R wherein ¹for organic radical);-O-and-S-; Consider cost and physical durability, more preferably-O-and-S-, most preferably be-O-.

Because there is the component units of formula (P1) due to electrophilic group Y ¹effect and chemical stability is good, and, in the time being formed as segmented copolymer, can improve physical strength and water resisting property, therefore can form strengthening three-dimensional network, realize good physical durability.

Consider physical durability and chemical stability, there is the component units of formula (P1) not good more greatly containing the ratio in sulfonic segment, be preferably 25 % by mole, more preferably 50 % by mole or more than, further be preferably 75 % by mole or more than, most preferably be 90 % by mole or more than.

Consider that raw material easily obtains, more preferably do not comprise containing the object lesson of the component units with formula (P1) contained in sulfonic segment (B2) there is following formula (P2-1), (P2) and (P4-1) to the component units of (P4-8).Consider physical strength, dimensional stability and the physical durability being produced by crystallinity, more preferably there is following formula (P2), (P4-1) or component units (P4-2), most preferably be the there is following formula component units of (P2).

Not good more greatly containing the content of the component units with following formula (P2) contained in sulfonic segment (B2), be preferably 25 % by mole or more than, more preferably 50 % by mole or more than, most preferably be 75 % by mole or more than.In the time that content is less than 25 % by mole, the effect of the present invention aspect physical strength, dimensional stability and the physical durability that produced by crystallinity is not good sometimes, is therefore not suitable for.

(Chemical formula 1 9)

(Chemical formula 2 0)

As not containing sulfonic segment (B2), the preferred example with the component units of wanting copolymerization beyond the component units of formula (P1) comprises: have the component units of the aromatic polyether polymkeric substance of ketone group containing, have following formula (q1) and do not contain sulfonic component units:

(Chemical formula 2 1)

In formula (q1), Z ¹with Z ²for the divalent organic base containing aromatic ring, they are each can be two or more group, but not containing sulfonic group.A and b are positive integer independently of one another.

As Z in formula (q1) ¹with Z ²shown preferred organic radical, more preferably Z ¹for phenylene, Z ²at least one for following formula (X-1), (X-2), (X-4) and (X-5).Organic radical can be replaced by the group beyond sulfonic group, still, considers from giving crystalline angle, and more preferably organic radical is not substituted.Z ¹with Z ²more preferably phenylene, most preferably is p-phenylene.

(Chemical formula 2 2)

Having formula (X-1), (X-2), (X-4) and group (X-5) can at random be replaced by the group beyond sulfonic group.

The preferred object lesson with the component units of formula (q1) includes but not limited to the to have following formula component units of (q2) to (Q7) etc., and the component units with formula (q1) can suitably be selected according to degree of crystallinity and physical strength.Consider degree of crystallinity and manufacturing cost, there is in the component units of formula (q1) more preferably following formula (q2), (Q3), (Q6) and (Q7), most preferably be formula (q2) and (Q7).

(Chemical formula 2 3)

Formula (q2) to (Q7), all with p-bit representation, still can comprise other binding site in the time that it has degree of crystallinity, as o-position or m-position.But, consider from crystalline angle, be preferably p-position.

The segmented copolymer further preferably being obtained by the present invention contain one or more containing sulfonic segment (B1) with do not contain the connection site being connected between sulfonic segment (B2).

In the present invention, linking agent (1inker) be defined as connect containing sulfonic segment (B1) with containing the position between sulfonic segment (B2), and have and be different from containing sulfonic segment (B1) and the chemical structure that does not contain sulfonic segment (B2).This linking agent, has suppressed due to chance mechanism, segment and side reaction that ether exchange reaction causes, but can connect different segments, therefore it is for obtaining segmented copolymer of being obtained by the present invention for most preferably.When without linking agent, occur as chance mechanisms such as segments in some situation, and cannot obtain fully effect of the present invention in some situation.

Be necessary for the compound that there is hyperergy, can in the randomization that suppresses to be caused by ether exchange reaction and segment (segment cutting), different segments be connected for linking agent of the present invention, it includes but not limited to decafluorobiphenyl, phenyl-hexafluoride, 4 at preferred object lesson of the present invention, 4 '-difluorodiphenyl base sulfone, 2,6-difluorobenzonitrile etc.In the time using as the polyfunctional linker such as decafluorobiphenyl or phenyl-hexafluoride, can prepare the segmented copolymer with branched structure by controlling reaction conditions.Simultaneously by change have formula (P1) unsulfonated segmented polymer and there is the preparation composition of the polymkeric substance of the sulfonation segment of formula (P2), also can prepare respectively the segmented copolymer of linear structure and there is the segmented copolymer of branched structure.

Below explanation is synthetic of the present invention containing sulfonic aromatics (M1) and method (M2).

Of the present inventionly be characterized as 2 sulfonic groups are introduced in a phenyl ring containing sulfonic aromatics, and increase partly sulfonic group density.Known to sulfonation reaction is electrophilic substitution reaction to phenyl ring, become extremely low therefore introduce the reactivity of sulfonic phenyl ring.Therefore, the almost not research of this part in prior art.

For phenyl ring being reached to two sulfonation, the present invention has carried out in depth research, found that, the pyroreaction that suppresses sulphur trioxide volatilization and carry out is conducive to carry out two sulfonation reactions on phenyl ring, and there is hardly side reaction, further can remove the inorganic salt in by product by recrystallization, further successfully obtain highly purified containing sulfonic aromatics.But, synthetic be not of the present inventionly limited containing sulfonic aromatics (M1) and method (M2).

Prepare a preparation method who contains sulfonic aromatics, comprise the step of being reacted with oleum by the aromatics of following general formula (M2) expression; Wherein, temperature of reaction is 120 ℃-250 ℃, adopts enclosed system and reacts adding to depress; Describedly contain sulfonic aromatics, its structure is as shown in general formula (M1):

(Chemical formula 2 4)

In formula (M1) and (M2), X ¹for ketone group, sulfuryl, direct connection ,-PO (R ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂in one; Each Y ¹independent is at least one in F, C1, Br and I; Each M ¹independent is hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom.M is 0 or 1; N is 0 or 1.

Y ¹comprise fluorine, chlorine, bromine and iodine, consider reactivity, preferably fluorine and chlorine, most preferably fluorine.Electron-withdrawing group X ¹comprise ketone group, sulfuryl, direct connection ,-PO (R ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(integer that wherein f is 1～5) or-C (CF ₃) ₂.Consider chemical stability and cost, preferably ketone group (CO-), sulfuryl (SO ₂-) or directly connect, further preferred ketone group and sulfuryl, by the viewpoint of physical durability, most preferably ketone group.Be most preferably X ¹for ketone group, Y ¹for F.

Considered R by chemical standpoint ¹be preferably at least one in hydroxyl, carboxyl, amido, halogen, alkyl, cycloalkyl, thiazolinyl, cycloalkenyl group, aryl, silylation, ester group, oxyalkyl, oxygen aryl, or derivatives thereof.By the viewpoint of structural stability, R ¹more preferably C1～C10 alkyl, C3-C10 cycloalkyl, aryl, containing sulfonic aryl, C1～C10 oxyalkyl, oxygen aryl, containing at least one in sulfonic oxygen aryl, or derivatives thereof.By the complexity that obtains this compound, R ¹more preferably aryl, containing at least one in sulfonic aryl, or derivatives thereof.Most preferably be containing sulfonic phenyl.

M ¹for metallic cation or ammonium cation, wherein metallic cation is preferably at least one in sodium, potassium, aluminium, magnesium, calcium, copper, nickel, cobalt, lead, zinc, tin, antimony, bismuth, silver, platinum, ruthenium, rhodium, palladium, osmium, tungsten, molybdenum, tantalum, niobium, zirconium, hafnium, vanadium, titanium, indium, thallium, germanium, selenium or tellurium ion.By the cost of initial compounds and the viewpoint of availability, more preferably sodium, potassium, aluminium, magnesium, calcium, copper, zinc or silver ions.

Of the present invention containing in the preparation method of sulfonic aromatics, temperature of reaction is 120 ℃-250 ℃, adopts enclosed system and reacts adding to depress.In airtight pressurized systems, the volatilization that plays on the one hand the sulphur trioxide of main sulfurization in oleum is restricted, and has guaranteed the concentration of sulphur trioxide in system; On the other hand, under pressure, intermolecular probability of collision increases, and has improved reaction efficiency.

Temperature of reaction is during lower than 120 ℃, and desired reaction almost can not be carried out; Temperature of reaction can cause during higher than 250 ℃ the degraded of raw material and product to occur.In the method for the invention, the reaction times, system was directly related with temperature of reaction, therefore not restriction especially.At high temperature need the shorter reaction times, need at low temperatures the reaction times of extremely growing.The control reaction times has being advisable containing sulfonic aromatics of formula (M2) obtaining.Reaction time range is preferably 1～48 hour.If the time is shorter than 1 hour, be difficult to obtain required compound; On the other hand, if the reaction times exceedes 48 hours, may cause the generation of the side reactions such as product decomposition.

In the method for the invention, closed system is resistance to pressure, thermotolerance and erosion resistance container, is preferably the pressure reaction still take tetrafluoroethylene (PTFE), silicon-dioxide, Kazakhstan formula alloy (hastelloy alloy) or titanium as liner.In the present invention, closed system also comprises the violent nitrogen gas stream of similar enclosed system, and as mentioned above, it is important suppressing sulphur trioxide evaporation and carrying out pyroreaction, and in fact violent nitrogen gas stream suppresses sulphur trioxide evaporation with sealed vessel similar effect.Utilize pressure reaction still with embodiment 17-27 explanation, utilize violent nitrogen gas stream system with embodiment 1～3 explanation.

In the method for the invention, reaction pressure is higher than normal pressure.Under normal pressure, be difficult to obtain the sulfonic aromatics that contains with formula (M2).In the method for the invention, to the reaction pressure upper limit unrestricted.But by the viewpoint of reaction safety, the higher reaction of reaction pressure is more dangerous.Because the method sulphur trioxide used has highly corrosive, and consider equipment cost, reaction pressure is preferably 0.12MPa to 50MPa, and more preferably 015MPa to 3.0MPa, most preferably is 0.2MPa to 1.5MPa.

In the method for the invention, in oleum, the concentration of sulphur trioxide is 20 % by weight to 65 % by weight.Commercially available oleum sulphur trioxide concentration is 20 % by weight to 65 % by weight scopes.

In the method for the invention, consider the complexity of substitution reaction occur, being preferably and showing formula (m3) under having containing sulfonic aromatics of formula (M1):

(Chemical formula 2 5)

In formula (m3), X is ketone group, sulfuryl, direct connection ,-PO (R ¹)-(be R wherein ¹for organic radical) ,-(CF ₂) _f-(wherein f is 1 to 5 integer) or-C (CF ₃) ₂in one; Y is at least one in F, Cl, Br or I; M is 0 or 1; N is 0 or 1; M is metallic cation or ammonium cation.

By the viewpoint of starting compound availability, X is preferably the one of ketone group or sulfuryl.The viewpoint of being lived by reaction, Y is preferably the one in F or Cl.

By the viewpoint of structural stability, R ¹more preferably C1～C10 alkyl, C3～C10 cycloalkyl, aryl, containing sulfonic aryl, C1～C10 oxyalkyl, oxygen aryl, containing the one in sulfonic oxygen aryl, or derivatives thereof.In addition, consider the availability of starting compound, be preferably aryl, contain at least one in sulfonic aryl, or derivatives thereof.M is metallic cation or ammonium cation.Cost and the availability of considering starting compound, be preferably the one in sodium, potassium, aluminium, magnesium, calcium, copper, zinc or silver.

By the viewpoint of cost and reactive behavior, what generate is preferably and shows formula (m4) under having containing sulfonic aromatics:

In formula (m4), M is metallic cation or ammonium cation.

M is preferably described above.

In the present invention, the step of reacting with oleum except thering is the aromatics of formula (M1), the method containing sulfonic aromatics that preparation has formula (M2) further comprises step (1) to (3):

(1) intermediate product obtaining after aromatics represented described general formula (M1) is reacted with oleum, neutralization then, and except desolventizing;

(2) with solvent, step (1) gained mixture is dissolved again, remove after insolubles, remove solvent;

(3) step (2) gained mixture is carried out to recrystallization.

Generate in the represented process that contains sulfonic aromatics of general formula (M2) in (M1) represented aromatics generation sulfurization, what play main sulfurization is the sulphur trioxide in oleum, so (M1) the use equivalent ratio of represented aromatics and sulphur trioxide will directly affect the structure of product.With respect to the represented aromatics of described general formula (M1), in oleum, the use equivalent of sulphur trioxide is 2～30 _:1.In oleum, the use equivalent of sulphur trioxide is low by 2 _:1, may not obtain general formula (M2) represented contain sulfonic aromatics; In oleum, the use equivalent of sulphur trioxide was higher than 30: 1, and sulphur trioxide is dense, may be unfavorable for aftertreatment.

Use oleum as reactant because preparing the represented process that contains sulfonic aromatics of general formula (M2), therefore finishing rear system, reaction is acid, thereby first system to be carried out to the described neutralizing treatment of step (1) to system pH value be 7.0-75, wherein, neutralization is alkali metal hydroxide with alkali, alkaline carbonate, at least one in alkali metal hydrocarbonate or ammonia, from cost of material and obtain the factor such as complexity and consider, described alkali is preferably sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, at least one of saleratus or ammoniacal liquor.

Preparation of the present invention is containing in the method for sulfonic aromatics, the solvent using in the dissolving again of step (2) is dimethyl sulfoxide (DMSO), sulfur oxychloride, 4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-dihydroxy diphenylsulphone, 4, at least one in 4 '-dimethylbenzene sulfoxide, tetramethylene sulfone, sulfobenzide or diphenyl sulfoxide.The factor of considering the each side such as character, price, toxicity of solvent itself, described solvent most preferably is dimethyl sulfoxide (DMSO).

Preparation of the present invention is containing in the method for sulfonic aromatics, and what step (2) was described removes insolubles by the sulfone class solution of obtained reaction product in the mode of precipitation, separation.Wherein be precipitated as: the sulfone class solution of obtained reactant is precipitated in alcohols or ketones solvent.Wherein said alcohol organic solvent is methyl alcohol, ethanol, Virahol, n-propyl alcohol, propyl carbinol, the trimethyl carbinol, isopropylcarbinol, sec-butyl alcohol, primary isoamyl alcohol, Pentyl alcohol, tertiary amyl alcohol, cyclopentanol, n-hexyl alcohol, hexalin, n-Octanol, secondary octanol, at least one in nonylcarbinol or phenylcarbinol; Organic solvent of ketone is at least one in acetone, butanone, methyl amylketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK) or pimelinketone.The factor of considering the each side such as character, price, toxicity of solvent itself, described alcohol organic solvent is preferably methyl alcohol or ethanol; Described organic solvent of ketone is preferably acetone.Described sepn process is: filtering separation or centrifugation.

Preparation of the present invention is containing in the method for sulfonic aromatics, and the described removal solvent of step (2) is drying process, is drying treatment 6-72 hour at 100-150 ℃.In order fully to remove the solvent and the preferred vacuum-drying of moisture that remain in sample.

Preparation of the present invention is containing in the method for sulfonic aromatics, and step (3) recrystallization, in deionized water, or in the mixing solutions of alcohols or organic solvent of ketone and deionized water, carries out at 4～25 ℃.Wherein the mixing solutions of alcohols or organic solvent of ketone and deionized water is alcohols or alcohol organic solvent and to go dried up volume ratio be 0～4: 1.

Can obtain the highly purified sulfonic aromatics that contains with formula (M1) by preparation method of the present invention, the content wherein with the aromatics of formula (M2) is 5 % by weight or following, by generated obtain containing sulfonic aromatics can obtain high loading capacity containing sulfonic group polymkeric substance and segmented copolymer, therefore its proton conductivity excellence, therefore can preferably be used.

There is sulfonic group at the segmented copolymer being obtained by the present invention, by the viewpoint of balance between proton-conducting and water tolerance, its loading capacity is preferably 0.1 to 5meq/ gram, further preferably 15meq/ gram or more than, further preferably 2meq/ gram or more than, most preferably 2.5meq/ gram.In addition, more preferably 4meq/ gram or following, further preferred 3.5meq/ gram or following, and the best is 3meq/ gram or following.When loading capacity is less than 01meq/ gram, in some situation proton-conducting deficiency, in the time that loading capacity is greater than 5meq/ gram, in some situation water tolerance deficiency.

In the segmented copolymer being obtained by the present invention, containing sulfonic segment (B1) with not containing the mol ratio (B1/B2) of sulfonic segment (B2) preferably 0.2 or more than, further preferably 0.33 or more than, most preferably 0.5 or more than.In addition, more preferably 5 or following, further preferably 3 or following, most preferably 2 or following.Be less than 0.2 or exceed at 5 o'clock at a mole ratio of components B1/B2, in some situation effect deficiency of the present invention, proton conductivity deficiency under low humidity condition, or in some situation hot water resistance and physical durability deficiency, therefore not preferred.

The ratio of the mole number of the repeating structure in mole number and the section of being present in (B2) that above-mentioned mol ratio (B1/B2) is the repeating structure in the section of being present in (B1).For example comprise containing sulfonic component units (S2) in section (B1), and when section (B1) comprises not containing sulfonic component units (P1), mol ratio represents the ratio divided by molecular weight value of acquisition of the component units corresponding to each other (S2) by the number-average molecular weight of each section.Be not with first polymkeric substance but when random copolymers, alternating copolymer or the segmented copolymer, mole proportion of composing represents the ratio divided by molecular-weight average value of acquisition of being calculated by each content molar ratio by the number-average molecular weight of each section at each section.

By the viewpoint of proton conductivity under low humidity condition, get over Gao Yuejia containing the loading capacity of sulfonic section (B1), be preferably 2.5meq/ gram or more than, more preferably 35meq/ gram or more than, most preferably be 4.5meq/ gram or more than.In addition, be preferably 7.5meq/ gram or following, further preferred 65meq/ gram or following, most preferably 5meq/ gram or following.In the time being less than 25meq/ gram containing the loading capacity of sulfonic segment (B1), proton-conducting deficiency under some situation low humidity condition, in the time that loading capacity exceedes 75meq/ gram, in some situation hot water resistance and physical durability deficiency, therefore not preferred.

Consider hot water resistance, physical strength, dimensional stability and physical durability, more low not good containing the loading capacity of sulfonic segment (B2), preferably 1meq/ gram or following, further preferred 05meq/ gram, most preferably 0.1meq/ gram or following.In the time not exceeding 1meq/ gram containing the loading capacity of sulfonic segment (B2), some situation hot water resistance, physical strength, dimensional stability, with physical durability deficiency, therefore not preferred.

The sulfonic molar weight that above-mentioned loading capacity is introduced for per unit net weight segmented copolymer, polymer electrolyte and polymer electrolyte film, the larger expression sulfonation degree of this value is higher.Loading capacity can be passed through the measurements such as elemental microanalysis method, neutralization titration.Loading capacity also can be used elemental microanalysis method to be calculated by S/C ratio, but this method is difficult to measure loading capacity in the time of the sulphur source of containing beyond sulfonic group.Therefore, in the present invention, loading capacity is defined as the numerical value obtaining by neutralization titration.Polymer electrolyte of the present invention and polymer electrolyte film system are the states of mixture, comprise the segmented copolymer and the aftermentioned constituent that are obtained by the present invention, so its loading capacity is to obtain based on mixture total amount.

Neutralization titration measuring method is as follows.This measurement carry out three times or more than, result is got its mean value.

(1) carry out proton exchange, the lip-deep moisture of the electrolytic thin-membrane that wiping has fully been cleaned with pure water, then by film in 100 ℃ of vacuum-dryings 12 hours or above and obtain its dry weight.

(2) dielectric film is added to the 5 % by weight aqueous sodium persulfate solutions of 50 milliliters, and left standstill 12 hours and implementation ion-exchange.

(3) sulfuric acid that uses the aqueous sodium hydroxide solution titration of 0.01 mol/L to produce.Add commercially available titration 0.1 weight/volume % phenolphthalein solution as indicator, and by solution become micro-red-be considered as terminal when purple.

(4) loading capacity calculates by following formula:

Loading capacity (meq/ gram)=(concentration (mmole/milliliter) × dripping quantity (milliliter) of aqueous sodium hydroxide solution)/sample dry weight (gram)

By polystyrene conversion, represent with weight-average molecular weight, the molecular weight of the segmented copolymer being obtained by the present invention is 50000 to 1000000, preferably 100000 to 500000.Being less than at 50000 o'clock at molecular weight,, there is slight crack in physical strength, physical durability and good solubility-resistence deficiency during as film forming.On the other hand, exceed at 1000000 o'clock at molecular weight, have poorly solublely, soltion viscosity is high, the problem of poor in processability.

Contain sulfonic segment (B1) to not relevant with the territory degree of phase separation structure containing the number-average molecular weight of sulfonic segment (B2), by the viewpoint of balance between proton-conducting and physical durability under low humidity condition, number-average molecular weight preferably 5000 or more than, further preferably 10000 or more than, most preferably 15000 or more than.In addition, more preferably 50000 or following, further preferably 40000 or following, most preferably 30000 or following.

The method that sulfonic group is introduced in segmented copolymer of the present invention comprises that polymerization has the method for sulfonic monomer or by polymer reaction, sulfonic group introduced to the method in segmented copolymer.

Polymerization has the method for sulfonic monomer, is to use in repeating unit, to have sulfonic monomer.This method is taken off and is set forth in Journal ofMembrane Science, 197,2002,231st～242 pages.This method is easily applied to industry, and to control the loading capacity of polymkeric substance, institute thinks most preferably.

Introducing sulfonic method by polymer reaction illustrates with example.By the method for aromatic polymer sulfonation, introduce sulfonic method, it takes off the method being set forth in No. 2-208322nd, for example No. 2-16126th, Japanese kokai publication hei or Japanese kokai publication hei.Particularly, can be by it is reacted in as chloroform equal solvent with as sulphonating agents such as chlorsulfonic acids to aromatic polymer, or aromatic polymer is reacted and sulfonation in the vitriol oil or oleum.Sulphonating agent is also not particularly limited, as long as can be by aromatic polymer sulfonation, except above-mentioned sulphonating agent also can use sulphur trioxide etc.In the time that aromatic polymer passes through this method sulfonation, sulfonation degree can pass through sulphonating agent usage quantity, temperature of reaction and reaction times and control.

The sulfonic group polymkeric substance that contains of the present invention is applicable to polymer electrolyte, and is specially adapted to polymer dielectric molding.In the present invention, polymer dielectric molding represents the molding that contains polymer electrolyte of the present invention.Determine according to application method, except film (comprising film and film shape), polymer dielectric molding of the present invention can be various ways, as plate, fiber, hollow yams, particle, agglomerate, micropore, coating and foam.Because polymkeric substance can freely design, and then can improve performances as various in physical strength and solvent resistance etc., can widespread use therefore should contain sulfonic group polymkeric substance.Particularly, should be applicable to polymer dielectric molding with form of film containing sulfonic group polymkeric substance.

In the time that polymer electrolyte of the present invention is applied to solid polymer type fuel battery, it is applicable to polymer electrolyte film, electrode catalyst layer etc.Wherein polymer electrolyte is applicable to polymer electrolyte film.Because in the time that polymer electrolyte is applied to solid polymer type fuel battery, it is usually used as polymer electrolyte film or the tamanori using filminess as electrode catalyst.

Polymer dielectric molding of the present invention can also have various uses.For example molding can be applicable to medicine (as extracorporeal circulation set tube and artificial skin), filtration, ion exchange resin (as chlorine resistance reverse osmosis membrane), various structured material, electrochemistry, humidification film, anti-fog film, antistatic film, solar battery thin film and gas barrier material.Also be suitable as artificial muscle and driver material.Wherein be preferably applied to various electrochemistry aspect.Electrochemical applications comprises fuel cell, redox flowing battery, apparatus for electrolyzing, chlor-alkali electrolyzer etc., wherein fuel cell most preferably.

Go on to say the preparation method who obtains polymer dielectric molding of the present invention.

Polymer dielectric molding of the present invention is formed containing the segmented copolymer of sulfonic segment (B2) (containing having formula (P2) component units) by not containing.Owing to not containing sulfonic segment (B2) for presenting the segment of degree of crystallinity; therefore polymer dielectric molding can first be shaped by protecting group is introduced to the segmented copolymer not containing in sulfonic segment (B2), then at least a portion protecting group contained molding is gone to protection and made.In segmented copolymer; not the polymkeric substance of random crystallization owing to there being the polymkeric substance of formative region on it; random crystallization can cause processibility to worsen; so preferably at least one protecting group is introduced containing in sulfonic segment (B2) to improve processibility, and preferably in the time of processibility variation, protecting group is introduced containing in sulfonic segment (B1).

Comprise for protecting group of the present invention the protecting group that is generally used for organic synthesis; and this protecting group is introduced (follow-up removable) and is protected the functional group with hyperergy for temporary transient; it is inactive substituting group to later reaction, and this functional group can remove to protect and revert back to original functional group after reaction.Be that protecting group can be matched with the functional group of need protection.As use the tertiary butyl as hydroxyl protecting group, but the identical tertiary butyl being introduced to the situation of stretching in alkyl chain, it is not called protecting group.Introduce the reaction of protecting group and be called protection (reaction), and the reaction that removes protecting group is called protection (reaction).

This protective reaction is specified in the Protective Groups in Organic Synthesis of Theodora W Greene, USA, and John Wiley & Sons, Inc., 1981, preferably use this reaction.About reactive behavior and the productive rate of protective reaction and protective reaction, contain the stability under protecting group state, manufacturing costs etc. can suitably be selected.The stage of introducing protecting group in polyreaction can be monomer stage, prepolymer stage or polymkeric substance stage, also can suitably select.

Protective reaction be by ketone position with ketal guarded by location/de-protected method, and by ketone position heteroatoms homologue (for example thio ketal ization) protection/de-protected method with ketal position.These methods are taken off the 4th chapter being set forth in Protective Groups in Organic Synthesis.In addition, it is included in protection/de-protected method between sulfonic acid and solubility ester derivative, the method that the tertiary butyl is introduced to the protection as solubility base in aromatic ring/go protection and with acid, this ring removed to tert-butylation.But protecting group is not limited, and as long as can preferably use for the group of protecting group.In order to improve the solubleness in solvent, by sterically hindered large viewpoint, preferably use fatty group, be specially fatty group containing circular part as protecting group.

Consider reactive behavior and stability; protective reaction further preferably makes ketone position become ketal position and protect/de-protected method, or makes ketone position become the heteroatoms homologue (for example thio ketal ization) of ketal position and protect/de-protected method.In polymer electrolyte of the present invention and polymer electrolyte film, containing the component units of protecting group preferably contain following formula (U1) and (U2) at least one:

(Chemical formula 2 6)

In formula (U1) and (U2), Ar ₉-Ar ₁₂for divalence is stretched aryl, R ₁with R ₂for at least one in H and alkyl, R ₃for stretching alkyl, E is O or S, its be respectively two kinds or more than.Having formula (U1) and group (U2) can be substituted arbitrarily.

Wherein by viewpoints such as the smell of compound, reactive behavior, stability, most preferably formula (U1) and (U2) in the E method that is O, even if ketone position becomes the protection/de-protected method of ketal position.

Consider stability, the R in formula (U1) ₁with more preferably alkyl of R2, more preferably there is the alkyl of 1～6 carbon atom, most preferably be the alkyl with 1～3 carbon atom.By the viewpoint of stability, the R in formula (U2) ₃be preferably the alkyl of stretching with 1～7 carbon atom, most preferably be the alkyl of stretching with 1～4 carbon atom.R ₃include but not limited to-CH ₂cH ₂-,-CH (CH ₃) CH ₂-,-CH (CH ₃) CH (CH ₃)-,-C (CH ₃) ₂cH ₂-,-C (CH ₃) ₂cH (CH ₃)-,-C (CH ₃) ₂o (CH ₃) ₂-,-CH ₂cH ₂cH ₂-,-CH ₂c (CH ₃) ₂cH ₂-etc.

Consider stability (as hydrolytic resistance), there is formula (U1) and component units (U2) and more preferably use the component units at least with formula (U2).In addition R in formula (U2), ₃preferably for thering is the alkyl of stretching of 1～7 carbon atom, there is C _n1h _2n1the group of (wherein n1 is 1～7), by the viewpoint of stability and synthetic easiness, most preferably-CH ₂cH ₂-,-CH (CH ₃) CH ₂-or-CH ₂cH ₂cH ₂in at least one.

Formula (U1) and (U2) middle Ar ₉to Ar ₁₂preferred organic radical is for stretching phenyl, stretch naphthyl or stretching xenyl.These groups can be substituted arbitrarily.In the segmented copolymer being obtained by the present invention, can be obtained the viewpoint of easiness by solvability and raw material, more preferably Ar in formula (U2) ₁₁with Ar ₁₂be and stretch phenyl, most preferably Ar ₁₁with Ar ₁₂be the p-phenyl of stretching.

In the present invention, the described method take ketal protection ketone position is, the method for under sour catalyst exists, the lead compound with a ketone group being reacted with monofunctional and/or two functional alcohol.For example ketal monomer can be by as the solvent of aliphatic series or aromatic hydrocarbon, and under existing as the sour catalyst of hydrogen bromide, by 4,4 '-dihydroxyl diphenylketone (it is ketone forerunner) is prepared with the reacting of alcohol of monofunctional and/or two senses.This alcohol is the fatty alcohol with 1～20 carbon atom.Be included under the adjacent ester of alkyl (alkyl orthoester) and the existence of solid catalyst for the preparation of the modification method of ketal monomer of the present invention, by 4,4 '-dihydroxyl diphenylketone (it is ketone forerunner) reacts with two functional groups' alcohol.

In the present invention, at least a portion is gone to protection and transformed into the method for ketone position and be not particularly limited with the ketone position of ketal protection.It can be under heterogeneous or processing condition, under water and acid exist, carry out protective reaction, but by the viewpoint of physical strength, physical durability and solvent resistance, more preferably after being configured as film etc., carries out acid-treated method.Particularly, it can be thin film dipped in the spirit of salt aqueous solution or aqueous sulfuric acid and go protection by what be shaped, and can suitably select acid concentration and aqueous temperature.

The part by weight of the relative polymkeric substance of acidic aqueous solution is preferably 1 to 100 times, also can use more substantial water.Acid catalyst is preferably with the concentration of 0.1 to 50 % by weight of existing water and uses.Preferred acid catalyst comprises strong mineral acid, as spirit of salt, nitric acid, fluosulfonic acid and sulfuric acid, and strong organic acid, as p-toluenesulphonic acids and trifluoromethanesulfonic acid.Amount, the reaction pressure etc. of acid catalyst and excessive water can suitably be selected according to polymer film thickness etc.

As when thick 25 microns of the film, approximately the film of entirety all can by by thin film dipped in as the acidic aqueous solution of the 6N spirit of salt aqueous solution or 5 % by weight aqueous sulfuric acids, and be heated to 95 ℃ from room temperature and last 1 to 48 hour and easily go to protect.Or or even all in fact protecting groups can be gone to protection at 25 ℃ last 24 hours in the 1N spirit of salt aqueous solution time by thin film dipped.But, go protective condition not to be limited, and go protection can pass through sour gas, organic acid or thermal treatment and carry out.

Particularly, have formula (U1) and (U2) forerunner of the segmented copolymer of component units can be by react and synthesize with the aromatics nucleophilic substitution of the active dihalide compound of aromatic series, it uses respectively has following formula (U1-1) and compound (U2-1) as dihydric phenol compound.Having formula (U1) and component units (U2) can, derived from dihydric phenol compound or the active dihalide compound of aromatic series, still consider monomer reaction activity, preferably uses the component units derived from dihydric phenol compound.

(Chemical formula 2 7)

In formula (U1-1) and (U2-1), Ar ₉to Ar ₁₂for divalence is stretched aryl; R ₁with R ₂for at least one in H and alkyl; R ₃for stretching alkyl; And E is O or S.The compound with formula (U1-1) and formula (U2-1) can be substituted arbitrarily.

For preferred dihydric phenol compound of the present invention comprise there is formula (r1) to the compound of (r10) and derived from the derivative of these dihydric phenol compounds.By the viewpoint of stability, in these dihydric phenol compounds, more preferably there is the compound of formula (r4) to (r10), further preferably there is formula (r4), (r5) and compound (r9), most preferably there is the compound of formula (r4).

In the time being synthesized by aromatic series nucleophilic substitution reaction implementation prepolymer for segment of the present invention for acquisition, polymkeric substance can obtain by monomer hybrid reaction under basic cpd existence.Polymerization can be the temperature range of 0-350 ℃, is preferably at 50-250 ℃ and carries out.The trend that responds and can not fully carry out during lower than 0 ℃ in temperature, the trend in temperature higher than 350 ℃ of polymer degradations that happen occasionally.Reaction can, in solvent-free lower implementation, still preferably be carried out in solvent.Useable solvents includes but not limited to aprotic polar solvent, as N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-methyl-2-Pyrrolizidine ketone, dimethyl sulfoxide (DMSO), tetramethylene sulfone, 1,3-dimethyl-2-imidazolidine ketone, hexamethylphosphorictriamide etc., and can use the solvent that can be used as solvent stability in the reaction of aromatic series nucleophilic substitution.These organic solvents can be separately or are used with two kinds or above mixing.

Basic cpd comprises sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus etc., and can use basic cpd thereby the indefinite that can make aromatic diol become active phenoxide structure.In order to increase the nucleophilicity of phenoxide, it suitably adds as the crown ether of 18-hat-6.In some situation, sulfonic sodium ion or potassium ion are improved to the solvability in organic solvent with these crown ether coordinations, preferably use this crown ether.

In the reaction of aromatic series nucleophilic substitution, be by product at some situation water.In this situation, toluene etc. can be present in reactive system, no matter polymer solvent why, it can become azeotrope and move to system outside with water.In moving to the method for system outside, Jiang Shui also can use as the water-retaining agent of molecular sieve etc.

The entrainer of the water that is used for removing reaction water or during reaction introduce is generally any polymerization that do not hinder in fact, can carry out condistillation with water, and the non-active compound that can seethe with excitement between approximately 25 ℃～approximately 250 ℃.One entrainer comprises benzene,toluene,xylene, chlorobenzene, methylene dichloride, dichlorobenzene, trichlorobenzene, pimelinketone etc.Naturally, selecting boiling point is favourable lower than the entrainer of used dipolar solvent.Conventionally use entrainer, but in the time using high reaction temperature, for example 200 ℃ or higher temperature, particularly, in the time having rare gas element to be sprayed at continuously on reaction mixture, may not need.Conventionally wish to react under the inert atmosphere of anaerobic existence.

In solvent, carry out aromatic series nucleophilic substitution when reaction, preferred monomers feeds intake and the concentration that makes to generate polymkeric substance is 5 to 50 % by weight.There is extent of polymerization to have in concentration during lower than 5 % by weight to be difficult to the trend increasing.On the other hand, the too high trend of system viscosity that responds during higher than 50 % by weight in concentration, is difficult to carry out the aftertreatment of reaction product.

After polyreaction finishes, can solvent be removed from reaction soln by evaporation, as required cleaning residue, then obtain desired polymkeric substance.Or this polymkeric substance also can be by reaction soln being added polymer dissolution degree low and in solvent that by-product inorganic salts solubleness is high, thereby remove inorganic salt, and polymkeric substance precipitation is become to solid, and filtrate filtering is obtained.Optionally, by reclaimed polymkeric substance, water, alcohol or other solvent cleaning are also dry.In the time obtaining institute's phase molecular weight, halogenide or phenoxide terminal base can be stablized terminal base optionally reaction to form by introducing phenoxide or halogenide end-capping reagent.

In addition, the chemical structure containing sulfonic group polymkeric substance of the present invention is by infrared absorption spectrum 1,030～1,045cm-1 and 1,160～1,190cm ^-1s=O absorb, 1,130～1,250cm ^-1c-O-C absorb, 1,640～1,660cm ^-1c=O absorb wait and confirm, its proportion of composing is learnt by neutralization titration or the ultimate analysis of sulfonate radical.Its structure also can pass through NMR (Nuclear Magnetic Resonance) spectrum ( ¹h-NMR) confirm, as derive from 68～80ppm and belong to aromatic proton peak.Sulfonic location and sulfonic arrangement mode can pass through solution ¹³c-NMR or solid ¹³c-NMR confirms.

Next explanation is synthetic respectively contains one or above containing sulfonic segment (B1), containing sulfonic segment (B2) and connect the preparation method of the linking agent position of segment.But the present invention is not limited by it.

The segmented copolymer being obtained by the present invention can pass through synthetic segmented copolymer forerunner, then at least a portion protecting group contained in forerunner is gone protection and prepare.

Preparation is comprised by the method for segmented copolymer of the present invention and segmented copolymer precursor: the one that a. is dihalide linking agent and two ends in segment and/or the segment forerunner with formula (P1) that the segment with formula (S2) of hydroxyl and/or segment forerunner and two ends be hydroxyl is reacted, and then manufactures the method for segmented copolymer with another section of polymerization alternately; B. randomly polymerization two ends be the segment with formula (S2) of hydroxyl and/or segment forerunner, with two ends be hydroxyl the segment with formula (P1) and/or segment forerunner, prepare the method for segmented copolymer with dihalide linking agent; C. use and there is the segment of formula (S2) and/or segment forerunner's unsulfonated product is prepared segmented copolymer by method described in a or b, then sulfonic group is optionally introduced have formula (S2) method in segment and/or segment forerunner's unsulfonated product; And d. is in conjunction with method of a to c etc.By the alternative copolymerization control territory degree that is separated, and the viewpoint of the chemically stable segmented copolymer of preparation, wherein most preferred method is a.

Preferably the method for preparation segmented copolymer of the present invention at least comprises the following steps (1) to (4).Can obtain high molecular by these steps, and then can improved mechanical strength and weather resistance, introduce two kinds of segments by alternating copolymerization, in segmented copolymer, phase separation structure and territory degree can strictly be controlled, and then good proton conductivity under the low humidity condition obtaining.

(1) the synthetic step containing sulfonic segment (B1), its contain there is formula (S2) component units and/or become the forerunner's of (S2) component units that there is formula component units, and two ends all have hydroxyl;

(2) synthetic not containing the step of sulfonic segment (B2), its contain there is formula (P1) component units and/or become the forerunner's of (P1) component units that there is formula component units, and two ends all have hydroxyl;

(3) linking agent is introduced containing sulfonic segment (B1) or not containing the step in two terminal hydroxy group of sulfonic segment (B2);

(4) segment that the segment that the two ends that are aggregated in synthesized in (3) are linking agent and other two ends are hydroxyl, thereby the forerunner who prepares segmented copolymer and segmented copolymer.

In method a, the segment with formula (S2) that two ends are hydroxyl has as shown in the formula (H3-1) and structure (H3-2), and the segment reacting with dihalide linking agent comprises have following formula (H3-3) and structure (H3-4).But the present invention is not limited by it.

(Chemical formula 2 8)

In formula (H3-1), in (H3-4), halogen atom represents with F, and basic metal represents with Na and K, but halogen atom and basic metal can be not limited by it and use.Above formula is to assign for auxiliary understanding, may not positively show chemical structure, correct constituent, i.e. and the arrangement mode of the polymerization composition of polymkeric substance, position, quantity, sulfonic molecular weight etc., but be not limited by it.

In addition; in formula (H3-1) in (H3-4); ketal group (ketal group) as protecting group is introduced in each segment; but in the present invention; protecting group is introduced and had in the composition of high-crystallinity and low solubility; have formula (H3-1) and (H3-3) containing the base that may not need protection in sulfonic segment (B1); and by the viewpoint of weather resistance and dimensional stability, also can preferably use the segment without protecting group.

In with the illustrative segment of formula (H3-1), its can by by bisphenol component and aromatic series dihalide composition with (N ₁+ 1): N ₁react and the controlled prepolymer of synthetic molecular weight.The same in formula (H3-2).

Use the temperature of reaction of block copolymerization of linking agent preferably under 140 ℃ or the lower condition of heating.More preferably 80 ℃ or higher and 120 ℃ or lower.Adopt 120 ℃ or low reaction temperatures more, can suppress fully the polymer architecture chance mechanism causing due to ether exchange reaction.On the other hand, if adopt 180 ℃ or higher temperature, obtain the polymkeric substance with random structure.

At the segmented copolymer being obtained by the present invention, can be observed common external phase isolating construction with transmission electron microscope.Control the phase separation structure of segmented copolymer, containing sulfonic segment (B1) with not containing the state of aggregation of sulfonic segment (B2) with and shape, can make material still can realize under low moisture conditions good proton-conducting.Can utilize transmission electron microscope (TEM), atomic force microscope (AFM) decile phase separation isolating construction.

Polymer electrolyte film comprises the phase separation structure of the segmented copolymer being obtained by the present invention, is preferably continuous shape structure or sheet structure.Phase separation structure can occur comprising in two kinds or the above polymkeric substance of incompatible section, for example, by the polymkeric substance that contains sulfonic segment (B1) and do not form containing the segmented copolymer of sulfonic segment (B2), and its structural form is roughly divided into common continuous structure (M1), sheet structure (M2), tubular structure (m3) and four kinds of island structures (m4) (as shown in Figure 1).

This phase separation structure is taken off and is set forth in the Chemistry as Annual Review ofPhysical, the 41,1990,525th page etc.The microtexture or the shape that contain sulfonic segment (B1) and do not contain sulfonic segment (B2) by controlling these, even at low humidity, under cold condition, still can realize good proton-conducting, particularly, (M1) that is Fig. 1 in its structure or (M2) time, be total to continuous or sheet structure, it can form continuous proton conduction passage, simultaneously owing to containing the not degree of crystallinity containing sulfonic segment (B2) yardstick, and can realize not only, proton-conducting is good, and there is extremely excellent fuel-barrier, solvent resistance, physical strength, and the polymer electrolyte film of physical durability, therefore preferred.

On the other hand, even under (m3) of Fig. 1 or situation (m4), i.e. tubular structure or island structure, it also may form continuous proton conduction passage.But, two kinds of structures are time relatively not less than normal containing the ratio of sulfonic segment containing the ratio of sulfonic segment, or time relatively not less than normal containing the ratio of sulfonic segment containing the ratio of sulfonic segment, the structure that can form, in the former situation, sulfonic amount with proton-conducting definitely reduces, and particularly, for itself not form continuous proton conduction passage in island structure, therefore proton-conducting is bad; In the latter's situation, proton-conducting amount good but nonionic crystallized domains is little, and therefore fuel-barrier, solvent resistance, physical strength and physical durability are bad, and then cannot fully obtain effect of the present invention.

Comprise the polymer electrolyte film of the segmented copolymer being obtained by the present invention, preferably utilize TEM to amplify 50000 times and observe phase separation structure, take the measured average layer spacing of image processing or averaged particles spacing as 8 nanometers or above and 100 nanometers or following polymer electrolyte film.Particularly average layer spacing or averaged particles spacing are preferably 10 nanometers or above and 50 nanometers or following, most preferably 15 nanometers or above and 30 nanometers or following.Utilizing transmission electron microscope not observe phase separation structure, or average layer spacing or averaged particles spacing are while being less than 8 nanometer, due to the continuity deficiency of ionic channel, in some situation electroconductibility deficiency, therefore not preferred.In addition, in the time that interfloor distance exceedes 5000 nanometer, worsen in some situation physical strength and dimensional stability, therefore not preferred.

The segmented copolymer being obtained by the present invention is characterized as it to be had phase separation structure and has degree of crystallinity simultaneously, and degree of crystallinity detects with thermal different type scanning analysis instrument (DSC) or wide-angle x-ray diffraction.This segmented copolymer be have take the measured crystallization heat of thermal different type scanning analysis instrument as 0.1 joule/gram or more than, or take the measured degree of crystallinity of X-ray diffraction as 0.5% or above segmented copolymer.

In the present invention, " having degree of crystallinity " represents that polymkeric substance is crystallizable in the time improving temperature, has crystallizable character, or crystallization.Non-crystalline polymer represents the not polymkeric substance for crystalline polymer, or it does not carry out in fact the polymkeric substance of crystallization.Therefore,, even be crystalline polymer at polymkeric substance but do not carry out fully under the situation of crystallization, the state of polymkeric substance is non-crystalline state.

Polymer electrolyte of the present invention is become to the method for polymer electrolyte film and is not particularly limited, can be in the stage with protecting group (as ketal etc.) and manufacture the method for film by solution state or manufactured the method for film by molten state.The former can be dissolved in polymer electrolyte as described embodiments as in the solvent of N-methyl-2-Pyrrolizidine ketone, then solution casting is coated on sheet glass etc., then removes solvent and obtains the method for film.

For the manufacture of the solvent of film as long as it is then removable solvent of dissolve polymer electrolyte, can suitably use aprotic polar solvent, as N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-methyl-2-Pyrrolizidine ketone, dimethyl sulfoxide (DMSO), tetramethylene sulfone, 1, 3-dimethyl-2-imidazolidine ketone, with hexamethyl phosphine triamide, ester solvent, as gamma-butyrolactone and butylacetate, carbonate solvent, as carbonic acid is stretched ethyl ester and carbonic acid is stretched propyl ester, stretch alkane glycol one alkyl oxide, as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol Monomethyl ether, with propylene glycol monoethyl ether, or alcoholic solvent, as Virahol, water and composition thereof, preferably there is the aprotic polar solvent of highest solubility.In addition, in order to increase the solubleness containing sulfonic segment (B1), add as the crown ether of 18-hat-6-be also suitable.

In the present invention, using when segmented copolymer, selective solvent is also very important to phase separation structure, and the mixture that uses aprotic polar solvent and have a solvent of low polarity is also suitable method.

Preferably the modulated polymers soln with necessary solid substance concentration that is made into being filtered under normal pressure, or under pressure, filter and remove the foreign matter being present in polymkeric substance solution matter solution, is the method that obtains toughness film.Filtering material used herein is also not particularly limited, and glass filter or metallic filter all can.In the time filtering, preferably 1 micron or following of the minimum-value aperture of the strainer that polymers soln passes through.In the time of unexecuted filtration, foreign matter can pollute and cause film breaks or weather resistance deficiency, therefore not preferred.

Then preferably the sulfonic group that generates at least a portion metal-salt state in polymer electrolyte film is heat-treated.During with metal-salt behavior aggregate, preferably material is directly made to film, by film thermal processing at the polymer electrolyte that wish is used.The metal of metal-salt is as long as it is for forming the metal of sulfonate, by the viewpoint of price and contaminate environment, preferably Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, W etc., wherein more preferably Li, Na, K, Ca, Sr and Ba, further preferably Li, Na and K.

Preferably 80 to 350 ℃ of this heat treated temperature,, most preferably are 120 to 150 ℃ by further preferably 100 to 200 ℃.Heat treatment time preferably 10 seconds to 12 hours, further preferably 30 seconds to 6 hours, most preferably is 1 minute to 1 hour.In the time that thermal treatment temp is too low, physical strength and physical durability deficiency in some cases.On the other hand, in the time that thermal treatment temp is too high, there is in some cases the decomposition of thin-film material.At heat treatment time than 10 seconds thermal effectiveness deficiencies in short-term.On the other hand, thin-film material easily occurring in the time that heat treatment time is longer than 12 hours worsens.If desired, the polymer electrolyte film being obtained by thermal treatment can carry out proton exchange by impregnated in acidic aqueous solution.Be shaped via this method, polymer electrolyte film of the present invention balance acquisition proton-conducting and physical durability preferably.

By the method that transforms into film for the sub-electrolyte of polymkeric substance of the present invention be, prepare the film being formed by polymer electrolyte by above-mentioned steps, then will go protection to become ketone position with at least a portion ketone position of ketal protection.Can make film according to this method, the solubleness in the solution that contains the segmented copolymer that does not contain sulfonic segment is bad, and can obtain proton-conducting, physical strength and physical durability.

Suitably used thickness is preferably the polymer electrolyte film of the present invention of 1 to 2000 micron.In order to obtain the physical strength and the physical durability that are applicable to practical use, more preferably exceed the thickness of 1 micron, and in order to reduce sheet resistance, improve electric power and produce performance, be preferably less than the thickness of 2000 microns.The further preferable range of this film thickness is 3 to 50 microns, most preferably 10 to 30 microns.Film thickness can be by adjusting the coat-thickness control on strength of solution or substrate.In addition can, by one additive for polymer compound, as nucleator agent, fluidizer, stablizer, antioxidant and releasing agent, not affect within the scope of the object of the invention and can add.The polymer electrolyte film being obtained by the present invention can be in the scope of the various character of not negative impact, contains various polymkeric substance, elastomerics, filler, fine particle and various additive.Polymer electrolyte film can utilize the strengthenings such as capillary film, non-woven fabric, mesh.

In the time using polymer electrolyte film as fuel cell, the combining method of polymer electrolyte film and electrode is also not particularly limited, can apply currently known methods (for example Electrochemistry, 1985,53, chemical plating method described in the 269th page, the Electrochemical Science and Technology of J.Electrochem Soc., 1988,135, heat pressing type bound gas diffusion electrode described in 9, the 2209 pages etc.).

Solid polymer type fuel battery is to use hydrogen ion conductivity polymer electrolyte film as electrolytic thin-membrane, has catalyst layer, electrode base material and the spacer body structure of lamination in proper order on electrolytic thin-membrane both sides.Wherein catalyst layer is called to catalyst coating film (CCM) at the electrolytic thin-membrane (being the layer composition of catalyst layer/electrolytic thin-membrane/catalyst layer) of its both sides lamination, in addition, by catalyst layer and gas diffusion substrate on its both sides sequentially the electrolytic thin-membrane of lamination (layer that is gas diffusion substrate/catalyst layer/electrolytic thin-membrane/catalyst layer/gas diffusion substrate forms) be called electrode-electric solution matter film assembly (MEA).

As for the method for manufacturing this catalyst coating film, conventionally use the coating catalyst layer that forms catalyst layer on electrolytic thin-membrane to stick with paste constituent, then dry coating method.But this coating method causes the problem that electrolytic thin-membrane expands and is out of shape because of the solvent (as water or alcohol) being contained in slurry, and is difficult to form desired catalyst layer in electrolyte membrane surface.In addition, also can cause because electrolytic thin-membrane is exposed to high temperature at drying step the problem of the distortion such as the electrolytic thin-membrane thermal expansion causing.In order to overcome this problem, now propose on substrate, only to prepare in advance catalyst layer, then shift this catalyst layer, more for example pass through this, by the method for catalyst layer lamination on electrolytic thin-membrane (transfer method) (No. 2009-9910th, TOHKEMY).

Because the polymer electrolyte film being obtained by the present invention is that toughness is good because having degree of crystallinity solvent resistance, therefore to be particularly suitable at coating method be that any situation of transfer method is as the coated film of catalyst for it.

When MEA manufactures by hot pressing, its temperature and pressure can suitably be selected according to the thickness of electrolytic thin-membrane, catalyst layer and electrode base board and water-content.In the present invention, pressurization is bonded under state electrolytic thin-membrane is dry or that absorb water also feasible.Pressurization comprises that roll-in defines pressure and gap, and plate is pressed and defined pressure, is had the viewpoint of the thermolysis of sulfonic polymer materials by industrial productivity and inhibition, and pressurization is preferably carried out in the scope of 0 ℃ to 250 ℃.By the viewpoint of protection electrolytic thin-membrane and electrode; pressurize preferably faint as far as possible; under the situation of pressing at plate; preferably 10MPa or lower pressure; by the viewpoint that prevents anode and cloudy intereelectrode short-circuit, not carrying out the combination of heat-press step and electrode and electrolytic thin-membrane lamination are formed to fuel cell liquid is preference.In the situation of this method, electric power generator being repeated to have the electrolytic thin-membrane of inhibition to worsen (origin cause of formation that inference is location of short circuit) during as fuel cell, and the trend that improves of the weather resistance of fuel cell.

In addition, use polymer electrolyte of the present invention and polymer electrolyte film solid polymer type fuel battery application and be not particularly limited, preferably as the power supply source of moving body.Particularly, solid polymer type fuel battery preferably, as the power supply source of substitute and the stationary power generation device of portable apparatus of past one-level battery and secondary battery, comprises mobil phone, Personal Computer, PDA, TV, receiving set, music player, game machine, earphone, DVD player etc.; Various industrial human-like or animal-type robots; Power equipment, comprises wireless dust collector etc.; Toy; And moving body, comprise vehicle, for example electric bicycle, locomotive, automobile, bus and truck; Ship and electric car; Or the power supply that blendes together as past one-level battery or secondary battery is originated.

Embodiment

The present invention illustrates in greater detail by following examples, but the present invention is not subject to the restriction of these embodiment.In addition, measure the condition of various physical propertiess as follows:

(1) loading capacity

The loading capacity (meq/ gram) of per unit gram calculates by neutralization titration.

(2) proton conductivity

Film like sample be impregnated in 25 ℃ of pure water to 24 hours, then in the constant temperature and humidity cabinet that 80 ℃ and relative humidity are 25～95%, keep 30 minutes, recycling set potential alternating-current impedance method is measured proton conductivity.

Use the electrochemical measurement system (Solartron1287Electrochemical Interface and Solartron1255B Frequency Response Analyzer) of being manufactured by Solartron company as measuring apparatus, be fixed current potential impedance measurement by two-terminal method, obtain proton conductivity.Amplitude is made as 50 millivolts.Test sample is the film of 10 mm wides, 50 millimeters long.Measured material is manufactured by phenol resin, and the part of measurement is unclamped.Electrode uses platinum plate (thick 100 microns, 2 plates).Electrode is placed in to the front and back side of sample thin film with the interelectrode distance of 10 millimeters, makes parallel to each other and longitudinally orthogonal with sample thin film.

(3) number-average molecular weight, weight-average molecular weight

The number-average molecular weight of polymkeric substance and weight-average molecular weight are by gpc measurement.The HLC-8022GPC that use is manufactured by Dong Cao company is as the integrated equipment of ultraviolet rays detector and parallax refractometer, and (internal diameter is 6.0 millimeters to use 2 TSK gel SuperHM-H that manufactured by Dong Cao company, long 15 centimeters) as GPC test pole, in METHYLPYRROLIDONE solvent (containing the METHYLPYRROLIDONE solvent of 10mM lithiumbromide) with the sample concentration of 0.1 % by weight, the flow velocity that 0.2mL/ divides, and the temperature of 40 ℃ implementation measurement, obtain number-average molecular weight and weight-average molecular weight by standard substance polystyrene conversion.

(4) film thickness

The ID-C112 type digital display dial gauge that film thickness system is used three rich companies on the heavy comparer stand BSG-20 that is fixed on the manufacture of three rich companies to manufacture is measured.

(5) observe phase separation structure with transmission electron microscope (TEM)

Sample strip be impregnated in 2 % by weight acetic acid lead solutions of staining agent, leave standstill 24 hours at 25 ℃.Dyed processing sample is taken out, embed visible-light curing resin, with radiation of visible light 30 seconds, sample is shaped.

Use ultramicrotome to cut 100 nanometer thin sections in room temperature, thin section is covered with Cu grid, carry out tem observation.Observe and carry out under the acceleration voltage of 100kV, and with × 8,000, × 20,000 or × 100,000 image multiple shooting.Instrument is TEM H7100FA (Hitachi, Ltd's manufacture).

(6) bisphenol cpd purity check

Quantitative analysis is used gas chromatograph (GC) to carry out under the following conditions.

Analytical column: DB-5 (manufacture of J & W company), L=30 rice, Φ=053 millimeter, D=150 micron

Carrier: helium (linear speed=350cm/ second)

Analysis condition

300 ℃ of note sample temperature

320 ℃ of detected temperatures

Baking box 50 ℃ × 1 minute

10 ℃/min of speed

Final 300 ℃ × 15 minutes

SP was than 50: 1

(7) hot water resistance

The hot water resistance of electrolytic thin-membrane is to assess by measurement size velocity of variation in 95 ℃ of hot water.Electrolytic thin-membrane is cut into the bar shaped that is about 5 centimeters and wide approximately 1 centimeter, in 25 ℃ of water, floods 24 hours, with vernier caliper measurement length (L1).Electrolytic thin-membrane is flooded in 95 ℃ of water to 8 hours again with vernier caliper measurement length (L2), its dimensional change amplitude can arrive in naked-eye observation again.

(8) NMR (Nuclear Magnetic Resonance) spectrum (NMR)

Under following measuring condition, carry out ¹the measurement of H-NMR, to carry out structural confirmation and to confirm containing sulfonic component units.

Equipment: the EX-270 that JEOL company manufactures

Resonant frequency: 270MHz ( ¹h-NMP)

Measure temperature: room temperature

Dissolution solvent: DMSO-d6

Interior mark: TMS (0ppm)

Integral number of times: 16 times

Under following measuring condition, carry out solid-state ¹³the measurement of C-CP/MAS spectrum, confirms to have or not remaining ketal group.

Equipment: the CMX-300Infinity that Chemagnetics company manufactures

Measure temperature: room temperature

Interior mark: Si rubber (1.56ppm)

Measure core: 75.188829MHz

Pulse width: 90 ° of pulse waves, 45 microseconds

Pulse repetition time: ACQTM=003413 second, PD=9 second

Spectral width: 30.003kHz

Sample rotates: 7kHz

Duration of contact: 4 milliseconds

The starting material that use in embodiment are synthetic:

(synthesis example 1)

There is 2 of following formula (G1), 2-bis-(4-hydroxy phenyl)-DOX (K-DHBP) synthetic:

(Chemical formula 2 9)

To be equipped with agitator, temperature to take into account to add in 500 ml flasks of still tube 495 grams 4,4 '-dihydroxyl diphenylketone, the ethylene glycol of 134 grams, the trimethyl orthoformate of 969 grams and the p-toluenesulphonic acids monohydrate of 050 gram, by material dissolves.Then temperature is remained on to 78 to 82 ℃, mixture is stirred 2 hours.Then, interior temperature is increased to 120 ℃ gradually, heats until the distillation of methyl-formiate, methyl alcohol and trimethyl orthoformate stops completely.After being cooled to room temperature, reaction soln ethyl acetate is diluted, organic layer is cleaned with 100 milliliter of 5% wet chemical, layer is separated, and solvent is evaporated.Residue is added to the methylene dichloride of 80 milliliters and precipitated crystal, by its filtration and dry, obtain 52.0 grams 2,2-bis-(4-hydroxy phenyl)-DOX.Crystallization is carried out to GC analysis, record its be 99.8% 2,2-bis-(4-hydroxy phenyl)-DOX and 0.2% 4,4 '-dihydroxyl diphenylketone.

(synthesis example 2)

There is 3 of following formula (H1), 3 '-disulfonic acid-4,4 '-difluorodiphenyl base ketone disodium synthetic:

(chemical formula 30)

By 109.1 grams 4,4 '-difluorodiphenyl base ketone (Aldrich reagent) at 100 ℃ in 150 milliliters of oleum (50%S0 ₃) (with the reagent of light pure chemistry Industrial Co., Ltd production) middle reaction 10 hours.Then reactant is inserted in large water gaging slowly, with NaOH neutralization, then add 200 grams of sodium-chlor, precipitation synthetic product.By the precipitation filtering generating, with aqueous ethanolic solution recrystallization, obtain and there is 3 of formula (H1), 3 '-disulfonic acid-4,4 '-difluorodiphenyl base ketone disodium.Its purity is 99.3%.With ¹h-NMR confirms structure.Capillary electrophoresis for impurity (organic substance) and ion chromatography (inorganic substance) carry out quantitative analysis.

Embodiment 1

(thering is 3,5 of following formula (G2), 3 ', 5 '-tetrasulfonic acid-4,4 '-difluorodiphenyl base ketone, four sodium synthetic)

To adding 1091 gram 4,4 '-difluorodiphenyl base ketone in 1000 milliliters of 3 mouthfuls of flasks of outfit agitator and thickener

(Aldrich reagent), 210 milliliters of oleum (60%S0 ₃) (Aldrich reagent), then nitrogen brute force is passed into and connect the nitrogen conduit on thickener top and the bubbler of guiding system outside, 180 ℃ of reactions 24 hours.Pass into nitrogen by brute force, suppress sulphur trioxide evaporation.Again reactant is inserted in large water gaging slowly, with NaOH neutralization, by ethanol precipitation 3 times, sodium sulfate is removed, obtain have following formula (G2) containing sulfonic aromatics.With ¹h-NMR confirms structure.Do not measure raw material, two sulfonated products and three sulfonated products completely, obtain highly purified four sulfonated products.

(chemical formula 31)

Comparative example 1

No. 2007-84739 described method of TOHKEMY attempted the synthetic of formula (G2).Be about to 109.1 gram 4,4 '-difluorodiphenyl base ketone, 150 milliliters of oleum (50%S0 ₃), 50 grams of sulphur trioxides are 180 ℃ of reactions 24 hours.Then reactant is little by little inserted in large water gaging, it is neutralized with NaOH, then add 200 grams of sodium-chlor and precipitate synthetic product.Generation precipitation filtering is carried out to purifying.

4, two sulfonated products of 4 '-difluorodiphenyl base ketone are primary product, and confirm to have a small amount of three sulfonated products and four sulfonated products.As described in No. 2007-84739th, TOHKEMY, only obtain the mixture of two sulfonated products, three sulfonated products and four sulfonated products, cannot strictly select the molar weight of relative bis-phenol, and use this monomer mixture to be difficult to obtain high molecular weight product.Embodiment 2

(thering is 3,5 of following formula (G3), 3 ', 5 '-tetrasulfonic acid-4,4 '-dichloro diphenylsulfone, four sodium synthetic)

In 1000 milliliters of 3 mouthfuls of flasks that are equipped with agitator and thickener, add 143.6 gram 4,4 '-dichloro diphenylsulfone

(Aldrich reagent), 210 milliliters of oleum (60%S0 ₃) (Aldrich reagent), then nitrogen brute force is passed into and connect the nitrogen conduit on thickener top and the bubbler of guiding system outside, 200 ℃ of reactions 24 hours.Now violent mobile nitrogen suppresses sulphur trioxide volatilization.Reaction soln is little by little inserted in large water gaging and with after NaOH neutralization, by ethanol precipitation 3 times, sodium sulfate is removed, obtain the sulfonic aromatics that contains with following formula (G3).With ¹h-NMR confirms structure.It does not recognize raw material, two sulfonated products and three sulfonated products completely, obtains highly purified four sulfonated products.

(chemical formula 32)

Embodiment 3

(thering is 3,5 of following formula (G4), 3 ', 5 '-tetrasulfonic acid-4,4 '-difluoro biphenyl, four sodium synthetic)

In 1000 milliliters of 3 mouthfuls of flasks that are equipped with agitator and thickener, add 950 gram 4,4 '-DfBP (Aldrich reagent), 210 milliliters of oleum (60%S0 ₃) (Aldrich reagent), then nitrogen brute force is passed into and connect the nitrogen conduit on thickener top and the bubbler of guiding system outside, 160 ℃ of reactions 24 hours.Now violent mobile nitrogen suppresses sulphur trioxide volatilization.Reaction soln is little by little inserted in large water gaging and with after Na0H neutralization, by ethanol precipitation 3 times, sodium sulfate is removed, obtain the sulfonic aromatics that contains with following formula (G4).With ¹h-NMR confirms structure.It does not recognize raw material, two sulfonated products and three sulfonated products completely, obtains highly purified four sulfonated products.

(chemical formula 33)

Embodiment 4

(have following formula (G5) containing sulfonic group polymkeric substance)

(chemical formula 34)

In formula, * represents that above formula right-hand member is combined in this position with following formula left end.Following * all with.

Be equipped with agitator, nitrogen conduit and Dean-Sta _rin 500 milliliters of 3 mouthfuls of flasks of k separator, add 5.5 grams of salt of wormwood, 5.2 grams to derive from 2 of synthesis example 1,2-bis-(4-hydroxy phenyl)-1,3-dioxolane mixture, 2.2 gram 4,4 '-difluorodiphenyl base ketone, 6.3 grams derive from the 18-hat-6-ether containing sulfonic aromatics and 2.6 grams with formula (G2) of embodiment 1, in 50 milliliters of N-Methyl pyrrolidone (NMP)/40 milliliter toluene, carry out band water (dehydration) in 180 ℃, then improve temperature and remove toluene, carry out polyase 13 hour at 240 ℃.Carry out purifying with large water gaging by redeposition and obtain the precursor polymer with ketal group.This polymkeric substance has 220000 weight-average molecular weight.

25 % by weight N-Methyl pyrrolidone (NMP) solution castings that its dissolving are configured to precursor polymer are coated on glass substrate, and it is dried to 4 hours at 100 ℃, then under nitrogen, within 30 minutes, obtain film in 150 ℃ of thermal treatments.Splendid containing the solubleness of sulfonic group polymkeric substance before shaping.Last 24 hour with carry out proton exchange and protective reaction after by thin film dipped in 10 % by weight aqueous sulfuric acids at 25 ℃; be impregnated in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G5).

What have formula (G5) contains at it component units with formula (S1) that contains 100 % by mole in sulfonic component units containing sulfonic group polymkeric substance.

The film thickness generating is 25 microns, and the loading capacity measured by neutralization titration is 3.4meq/ gram, finds no ketal group residual.This film is self-support film, estimates transparent and even.This film has the proton conductivity of 410mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 1mS/cm under 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 5

(have following formula (G6) containing sulfonic group polymkeric substance)

(chemical formula 35)

In 500 milliliters of 3 mouthfuls of flasks of outfit agitator, nitrogen conduit and Dean-Stark separator, add 3.9 grams of salt of wormwood, 5.2 grams to derive from 2 of synthesis example 1,2-bis-(4-hydroxy phenyl)-1,3-dioxolane mixture, 1.3 gram 4,4 '-difluorodiphenyl base ketone, 8.8 grams derive from the 18-hat-6-ether containing sulfonic aromatics and 3.6 grams with formula (G2) of embodiment 1, in 50 milliliters of N-Methyl pyrrolidone (NMP)/40 milliliter toluene, carry out band water in 180 ℃, then improve temperature and remove toluene, carry out polyase 13 hour at 240 ℃.Carry out purifying with large water gaging by redeposition and obtain the precursor polymer with ketal group.This polymkeric substance has 200000 weight-average molecular weight.

25 % by weight N-Methyl pyrrolidone (NMP) solution castings that its dissolving are configured to precursor polymer are coated on glass substrate, and it is dried to 4 hours at 100 ℃, then under nitrogen, within 30 minutes, obtain film in 150 ℃ of thermal treatments.Splendid containing the solubleness of sulfonic group polymkeric substance before shaping.Last 24 hour with carry out proton exchange and protective reaction after by thin film dipped in 10 % by weight aqueous sulfuric acids at 25 ℃; be impregnated in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G6)

Containing in sulfonic component units, what have formula (G6) is to contain 100 % by mole of component units with formula (S1) containing sulfonic group polymkeric substance.

25 microns of film former thickness, the loading capacity being obtained by neutralization titration is 4.2meq/ gram, and identification does not have ketal group residual.This film is self-support film, estimates transparent and even.This film has the proton conductivity of 700mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 15mS/cm at 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 6

(have following formula (G7) containing sulfonic group polymkeric substance)

(chemical formula 36)

In 500 milliliters of 3 mouthfuls of flasks of outfit agitator, nitrogen conduit and Dean-Stark separator, add 3.3 grams of salt of wormwood, 5.2 grams to derive from 2 of synthesis example 1,2-bis-(4-hydroxy phenyl)-1,3-dioxolane mixture, 3.1 gram 4,4 '-difluorodiphenyl base ketone, 3.8 grams derive from the 18-hat-6-ether containing sulfonic aromatics and 1.6 grams with formula (G2) of embodiment 1, in 50 milliliters of N-Methyl pyrrolidone (NMP)/40 milliliter toluene, carry out band water in 180 ℃, then improve temperature and remove toluene, carry out polyase 13 hour at 240 ℃.Carry out purifying with large water gaging by redeposition and obtain the precursor polymer with ketal group.This polymkeric substance has 280000 weight-average molecular weight.

25 % by weight N-Methyl pyrrolidone (NMP) solution castings that its dissolving are configured to precursor polymer are coated on glass substrate, and it is dried to 4 hours at 100 ℃, then under nitrogen, within 30 minutes, obtain film in 150 ℃ of thermal treatments.Splendid containing the solubleness of sulfonic group polymkeric substance before shaping.Last 24 hour with carry out proton exchange and protective reaction after by thin film dipped in 10 % by weight aqueous sulfuric acids at 25 ℃; be impregnated in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G7)

Containing in sulfonic component units, what have formula (G7) is to contain 100 % by mole of component units with formula (S1) containing sulfonic group polymkeric substance.

25 microns of film former thickness, the loading capacity being obtained by neutralization titration is 2.4meq/ gram, and identification does not have ketal group residual.This film is self-support film, estimates transparent and even.This film has the proton conductivity of 350mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 05mS/cm at 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 7

(have following formula (G8) containing sulfonic group polymkeric substance)

(chemical formula 37)

According to same procedure as described in Example 4, carry out polymerization and obtain the polymkeric substance containing sodium sulfonate group, wherein with 3.2 grams 2,6-dihydroxy naphthlene replaces and derives from 2 of synthesis example 1,2-bis-(4-hydroxy phenyl)-DOX mixture.This polymkeric substance has 170000 weight-average molecular weight.

According to same procedure as described in Example 4, generated polymkeric substance is carried out to film forming.Good containing the solubleness of sulfonic group polymkeric substance before shaping.25 ℃ by thin film dipped in 10 % by weight aqueous sulfuric acid 24 hours to carry out after proton exchange, be impregnated in again in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G8).

Containing in sulfonic component units, what have formula (G8) is to contain 100 % by mole of component units with formula (S1) containing sulfonic group polymkeric substance.

25 microns of film former thickness, the ion-exchange power capacity being obtained by neutralization titration is 33meq/ gram, and identification does not have ketal group residual.This film is self-support film, estimates transparent and even.This film has the proton conductivity of 380mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 08mS/cm at 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 8

(have following formula (G9) containing sulfonic group polymkeric substance)

(chemical formula 38)

According to same procedure as described in Example 4, carry out polymerization and obtain the polymkeric substance containing sodium sulfonate group, wherein replace and derive from 2 of synthesis example 1,2-bis-(4-hydroxy phenyl)-DOX mixture with 4, the 4 '-'-biphenyl diphenol of 3.7 grams.This polymkeric substance has 160000 weight-average molecular weight.

According to same procedure as described in Example 4, generated polymkeric substance is carried out to film forming.Good containing the solubleness of sulfonic group polymkeric substance before shaping.25 ℃ by thin film dipped in 10 % by weight aqueous sulfuric acid 24 hours to carry out after proton exchange, be impregnated in again in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G9).

Containing in sulfonic component units, what have formula (G9) is to contain 100 % by mole of component units with formula (S1) containing sulfonic group polymkeric substance.

25 microns of film former thickness, the ion-exchange power capacity being obtained by neutralization titration is 3.3meq/ gram, and identification does not have ketal group residual.This film is self-support film, estimates transparent and even.This film has the proton conductivity of 370mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 0.7mS/cm at 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 9

(have following formula (G10) containing sulfonic group polymkeric substance)

(chemical formula 39)

According to same procedure as described in Example 4, carry out polymerization and obtain the precursor polymer with ketal group, wherein 7.0 grams of sulfonic aromatics that contain with formula (G3) that derive from embodiment 2 replace the sulfonic aromatics that contains with formula (G2) that derives from embodiment 1.This polymkeric substance has 200000 weight-average molecular weight.

According to same procedure as described in Example 4, generated polymkeric substance is carried out to film forming.Splendid containing the solubleness of sulfonic group polymkeric substance before shaping.25 ℃ by thin film dipped in 10 % by weight aqueous sulfuric acid 24 hours to carry out after proton exchange and protective reaction; be impregnated in again in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G10).

Containing in sulfonic component units, what have formula (G10) is to contain 100 % by mole of component units with formula (S1) containing sulfonic group polymkeric substance.

25 microns of film former thickness, the ion-exchange power capacity being obtained by neutralization titration is 3.5meq/ gram, and identification does not have ketal group residual.This film is self-support film, estimates transparent and even.This film has the proton conductivity of 360mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 0.65mS/cm at 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 10

(have following formula (G11) containing sulfonic group polymkeric substance)

(chemical formula 40)

According to same procedure as described in Example 4, carry out polymerization and obtain the precursor polymer with ketal group, wherein 6.0 grams of sulfonic aromatics that contain with formula (G4) that derive from embodiment 2 replace the sulfonic aromatics that contains with formula (G2) that derives from embodiment 1.This polymkeric substance has 190000 weight-average molecular weight.

According to same procedure as described in Example 4, generated polymkeric substance is carried out to film forming.Splendid containing the solubleness of sulfonic group polymkeric substance before shaping.25 ℃ by thin film dipped in 10 % by weight aqueous sulfuric acid 24 hours to carry out after proton exchange and protective reaction; be impregnated in again in greatly excessive pure water 24 hours to clean fully film, obtain thus and comprise the there is formula polymer electrolyte film containing sulfonic group polymkeric substance of (G11).

Containing in sulfonic component units, what have formula (G11) is to contain 100 % by mole of component units with formula (S1) containing sulfonic group polymkeric substance.

25 microns of film former thickness, the loading capacity being obtained by neutralization titration is 3.6meq/ gram.Although it is weaker but still for self-support film, estimate transparent and even that this film is compared the film of embodiment 4.This film has the proton conductivity of 350mS/cm under 80 ℃, 85% relative humidity, has the proton conductivity of 0.6mS/cm at 80 ℃, 25% relative humidity, and under its low humidity, proton conductivity is good.

Embodiment 11

(thering is not the synthesizing containing sulfonic prepolymer a1 ' of following formula (G12))

In 1000 milliliters of 3 mouthfuls of flasks that are equipped with agitator, nitrogen conduit and Dean-Stark separator, add 16.59 grams of salt of wormwood (Aldrich reagent, 120 mmoles), 25.8 grams (100 mmole) derive from the K-DHBP, 20.3 gram 4 of synthesis example 1,4 '-difluorodiphenyl base ketone (Aldrich reagent, 93 mmoles), with nitrogen replacement, then in the toluene of 300 milliliters of N-Methyl pyrrolidone (NMP) and 100 milliliters, carry out band water in 160 ℃, rear raising temperature to be to remove toluene, then carries out polymerizations 1 hour in 180 ℃.Carry out deposition and purification and obtain the not prepolymer a1 containing sulfonic group (end group is as hydroxyl) take a large amount of methyl alcohol.This prepolymer has 10000 number-average molecular weight.

In 500 milliliters of 3 mouthfuls of flasks that are equipped with agitator, nitrogen conduit and Dean-Stark separator, add 1.1 grams of salt of wormwood (Aldrich reagent, 8 mmoles), 20.0 grams (2 mmole) containing the prepolymer a1 of sulfonic group (end group is hydroxyl), then nitrogen replacement, in 100 milliliters of N-Methyl pyrrolidone (NMP) and 30 milliliters of hexanaphthenes, carry out band water in 100 ℃, then improve temperature to remove hexanaphthene, and add the decafluorobiphenyl (Aldrich reagent, 12 mmoles) of 4.0 grams at 105 ℃, to react 1 hour.Take a large amount of Virahols carry out deposition and purification and obtain there is following formula (G12) not containing the prepolymer a1 ' of sulfonic group (end group is as fluorine).This prepolymer has 11000 number-average molecular weight, and the difference that is not 10400, two values containing the number-average molecular weight of the sulfonic prepolymer a1 molecular weight (molecular weight is 630) that is linking agent.

(chemical formula 41)

(thering is the synthesizing containing sulfonic prepolymer a2 of following formula (G13))

Be equipped with agitator, in 1000 milliliters of 3 mouthfuls of flasks of nitrogen conduit and Dean-Stark separator, add 41.5 grams of salt of wormwood (Aldrich reagent, 300 mmoles), 129 grams (50 mmoles) derive from the K-DHBP of synthesis example 1, 9.3 gram 4, 4 '-'-biphenyl diphenol (Aldrich reagent, 50 mmoles), 583 grams (93 mmole) derives from the sulfonic aromatics that contains of embodiment 1, and 491 grams of 18-hats-6 are (with light pure chemistry Industrial Co., Ltd product, 186 mmoles), with nitrogen replacement, then in 400 milliliters of N-Methyl pyrrolidone (NMP) and 150 milliliters of toluene, carry out band water in 170 ℃, improve subsequently temperature to remove toluene, carry out polymerization 1 hour at 220 ℃.Obtain take a large amount of isopropanol precipitating purifying there is following formula (G13) containing the prepolymer a2 of sulfonic group (end group is as hydroxyl).This prepolymer has 16000 number-average molecular weight.

(chemical formula 42)

In formula (G13), M is Na or K.Following M is all identical.

(prepolymer a2 as containing sulfonic segment (B1), prepolymer a1 as not stretching synthetic as the segmented copolymer b1 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

In 500 milliliters of 3 mouthfuls of flasks that are equipped with agitator, nitrogen conduit and Dean-Stark separator, add 0.56 gram of salt of wormwood (Aldrich reagent, 4 mmoles), 16 grams (1 mmole) containing the prepolymer a2 of sulfonic group (end group is hydroxyl), with nitrogen replacement, then in 100 milliliters of N-Methyl pyrrolidone (NMP) and 30 milliliters of hexanaphthenes, be with water in 100 ℃, rear raising temperature is to remove hexanaphthene, and add 11 grams (1 mmoles) not containing sulfonic group (end group is fluorine) prepolymer a1 ', at 105 ℃, react 24 hours.Obtain segmented copolymer b1 with a large amount of isopropanol precipitating purifying.This segmented copolymer has 230000 weight-average molecular weight.

Use glass fibre filter, 25 % by weight N-Methyl pyrrolidone (NMP) solution to segmented copolymer b1 carry out pressure filtration, and curtain coating is coated on glass substrate, it is dried to 4 hours at 100 ℃, then obtains polyketals-one film (thick 25 microns) in 150 ℃ of thermal treatments 10 minutes under nitrogen atmosphere.The solvability of polymkeric substance is splendid.Carry out proton exchange and protective reaction at 95 ℃ by thin film dipped 24 hours in 10 % by weight aqueous sulfuric acids, be then impregnated in again in greatly excessive pure water 24 hours fully to clean film, obtain thus polymer electrolyte film.

Containing in sulfonic component units, the component units with formula (S1) that this film contains 100 % by mole.The loading capacity that this film is obtained by neutralization titration is 25meq/ gram, and identification does not have ketal group residual.This film is the electrolytic thin-membrane that has toughness, and estimates transparent, even.The proton conductivity of this film is 900mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 50mS/cm, and its low humidity proton-conducting is good.In addition, the size changing rate of this film is low to moderate 15%, and hot water resistance is also good.

In addition, tem observation can confirm to have the common external phase isolating construction that territory degree is 25 nanometers.Contain sulfonic territory and all do not form external phase containing sulfonic territory.

Embodiment 12

(thering is not the synthesizing containing sulfonic prepolymer a3 ' of formula (G6))

With reference to the method described in embodiment 11, and synthetic not containing the prepolymer a3 of sulfonic group (end group is hydroxyl), wherein by 4, the charging capacity of 4 '-difluorodiphenyl base ketone makes 207 grams (Aldrich reagent, 95 mmoles) into.This prepolymer has 15000 number-average molecular weight.

With reference to the method described in embodiment 11, and the synthetic prepolymer a3 ' that does not contain sulfonic group (end group is fluorine) with formula (G12), that wherein utilizes 300 grams (2 mmoles) does not replace the prepolymer a1 containing sulfonic group (end group is hydroxyl) containing the prepolymer a3 of sulfonic group (end group is hydroxyl).This prepolymer has 16000 number-average molecular weight, and is not 15400 containing the number-average molecular weight of sulfonic prepolymer a3, and both differences are by due to linking agent (molecular weight is 630).

(thering is the synthetic containing sulfonic prepolymer a4 of formula (G13))

With reference to method described in embodiment 11, acquisition has the prepolymer a4 containing sulfonic group (end group is hydroxyl) of formula (G13), wherein make the charging capacity containing sulfonic aromatics that derives from embodiment 1 into 59.5 grams (95 mmoles), the charging capacity of bis-phenol makes 25.8 grams of (100 mmole) K-DHBP into, and a4 prepolymer has 21000 number-average molecular weight.

(prepolymer a4 as containing sulfonic segment (B1), prepolymer a3 as not stretching synthetic as the segmented copolymer b2 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

With reference to method described in embodiment 11, and acquisition segmented copolymer b2, wherein replace the prepolymer a2 containing sulfonic group (end group is as hydroxyl) take the prepolymer a4 containing sulfonic group (end group is as hydroxyl) of 21 grams (1 mmoles), and replace the not prepolymer a1 ' containing sulfonic group (end group is as fluorine) take the prepolymer a3 ' that does not contain sulfonic group (end group is as fluorine) of 16 grams (1 mmoles).B2 segmented copolymer has 250000 weight-average molecular weight.

Configuration segmented copolymer b2 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, the component units with formula (S1) that this film contains 100 % by mole.The loading capacity that this film is obtained by neutralization titration is 2.2meq/ gram, and identification does not have ketal group residual.This film is the self-support film that has toughness, and estimates transparent, even.The proton conductivity of this film is 600mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 20mS/cm, and its low humidity proton-conducting is good.In addition, this film dimensions velocity of variation is low to moderate 10%, and hot water resistance is also good.

In addition, tem observation can confirm to have the common external phase isolating construction that territory degree is 35 nanometers.Contain sulfonic territory and all do not form external phase containing sulfonic territory.

Embodiment 13

(thering is not the synthesizing containing sulfonic prepolymer a5 ' of formula (G12))

With reference to method described in embodiment 11, and synthetic not containing the prepolymer a5 of sulfonic group (end group is hydroxyl), wherein by 4, the charging capacity of 4 '-difluorodiphenyl base ketone makes 207 grams (Aldrich reagent, 95 mmoles) into.A5 prepolymer has 15000 number-average molecular weight.

With reference to method described in embodiment 11, the synthetic prepolymer a5 ' that does not contain sulfonic group (end group is fluorine) with formula (G12), wherein replaces the prepolymer a1 containing sulfonic group (end group is as hydroxyl) take the prepolymer a5 that does not contain sulfonic group (end group is as hydroxyl) of 300 grams (2 mmoles).A5 ' prepolymer has 16000 number-average molecular weight, and is not 15400 containing the number-average molecular weight of sulfonic prepolymer a5, and both differences are due to linking agent (molecular weight is 630).

(containing synthesizing of sulfonic prepolymer a6)

With reference to method described in embodiment 11, preparation is containing the prepolymer a6 of sulfonic group (end group is hydroxyl), wherein make the charging capacity containing sulfonic aromatics that derives from embodiment 1 into 300 grams (475 mmoles), and what add that 20.1 grams (47.5 mmoles) derive from synthesis example 2 has 3 of a formula (H1), 3 '-disulfonic acid-4,4 '-difluorodiphenyl base ketone disodium, makes the charging capacity of K-DHBP into 25.8 grams (100 mmoles).A6 prepolymer has 20000 number-average molecular weight.

(prepolymer a6 as containing sulfonic segment (B1), prepolymer a5 as not stretching synthetic as the segmented copolymer b3 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

With reference to method described in embodiment 11, obtain segmented copolymer b3, wherein replace the prepolymer a2 containing sulfonic group (end group is as hydroxyl) take the prepolymer a6 containing sulfonic group (end group is as hydroxyl) of 20 grams (1 mmoles), and replace the not prepolymer a1 ' containing sulfonic group (end group is as fluorine) take the prepolymer a5 ' that does not contain sulfonic group (end group is as fluorine) of 16 grams (1 mmoles).B3 segmented copolymer has 320000 weight-average molecular weight.

Configuration segmented copolymer b3 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, this film contains 50 % by mole of component units with formula (S1).The loading capacity that this film is obtained by neutralization titration is 1.8meq/ gram, and identification does not have ketal group residual.This film is the self-support film that has toughness, estimates transparent, even.The proton conductivity of this film is 450 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 9 mS/cm, and its low humidity proton-conducting is good.In addition, this film dimensions velocity of variation is low to moderate 7%, and hot water resistance is also good.

In addition, tem observation can confirm to have the common external phase isolating construction that territory degree is 30 nanometers.Contain sulfonic territory and all do not form external phase containing sulfonic territory.

Embodiment 14

(thering is not the synthesizing containing sulfonic prepolymer a7 ' of formula (G12))

With reference to method described in embodiment 11, synthetic not containing the prepolymer a5 of sulfonic group (end group is hydroxyl), wherein by 4, the charging capacity of 4 '-difluorodiphenyl base ketone makes 20 7 grams of (Aldrich reagent into, 95 mmoles), a5 prepolymer has 15000 number-average molecular weight.

With reference to method described in embodiment 11, the synthetic prepolymer a5 ' that does not contain sulfonic group (end group is fluorine) with formula (G12), wherein replace the prepolymer a1 containing sulfonic group (end group is as hydroxyl) take the prepolymer a5 that does not contain sulfonic group (end group is as hydroxyl) of 30.0 grams (2 mmoles), a5 ' prepolymer has 16000 number-average molecular weight, and be not 15400 containing the number-average molecular weight of sulfonic prepolymer a5, both differences are by due to linking agent (molecular weight is 630).

(containing synthesizing of sulfonic prepolymer a8)

With reference to method described in embodiment 11, the synthetic prepolymer a6 containing sulfonic group (end group is hydroxyl), wherein make the charging capacity containing sulfonic aromatics that derives from embodiment 1 into 17 9 grams (28 5 mmoles), and what add that 28.1 grams (66.5 mmoles) derive from synthesis example 2 has 3 of a formula (H1), 3 '-disulfonic acid-4,4 '-difluorodiphenyl base ketone disodium, the charging capacity of K-DHBP makes 25 8 grams (100 mmoles) into, and the prepolymer obtaining has 19000 number-average molecular weight.

(prepolymer a6 as containing sulfonic segment (B1), prepolymer a5 as not stretching synthetic as the segmented copolymer b4 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

With reference to method described in embodiment 11, synthetic segmented copolymer b4, wherein replace the prepolymer a2 containing sulfonic group (end group is as hydroxyl) take the prepolymer a8 containing sulfonic group (end group is as hydroxyl) of 19 grams (1 mmoles), and replacing the prepolymer a1 ' containing sulfonic group (end group is as fluorine) take the prepolymer a7' that does not contain sulfonic group (end group is as fluorine) of 16 grams (1 mmoles), b4 segmented copolymer has 360000 weight-average molecular weight.

Configuration segmented copolymer b4 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, this film contains 30 % by mole of component units with formula (S1).The loading capacity that this film is obtained by neutralization titration is 1.7 meq/ gram, and identification does not have ketal group residual.This film is the self-support film that has toughness, estimates transparent, even.The proton conductivity of this film is 250 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 2 mS/cm, and its low humidity proton-conducting is good.In addition, this film dimensions velocity of variation is low to moderate 6%, and hot water resistance is also good.

Embodiment 15

(thering is not the synthesizing containing sulfonic prepolymer a9 ' of following formula (G14))

With reference to method described in embodiment 11, synthetic not containing the prepolymer a9 ' of sulfonic group (end group is fluorine), wherein with 26.7 grams (93 mmoles) 4,4 '-dichloro diphenylsulfone replaces 4,4 '-difluorodiphenyl base ketone.This prepolymer has 11000 number-average molecular weight, and is not 10400 containing the number-average molecular weight of sulfonic prepolymer a9, and both differences are by due to linking agent (molecular weight is 630).

(chemical formula 43)

(prepolymer a2 as containing sulfonic segment (B1), prepolymer a9 as not stretching synthetic as the segmented copolymer b5 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

With reference to method described in embodiment 11, prepare segmented copolymer b5, wherein replace the prepolymer ar containing sulfonic group (end group is as fluorine) take the prepolymer a9' that does not contain sulfonic group (end group is as fluorine) of 11 grams (1 mmoles).Segmented copolymer b5 has 200000 weight-average molecular weight.

Configuration segmented copolymer b5 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, this film contains 100 % by mole of component units with formula (S1).The loading capacity that this film is obtained by neutralization titration is 23 meq/ gram, and identification does not have ketal group residual.This film is the self-support film that has toughness, estimates transparent, even.The proton conductivity of this film is 650 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 10 mS/cm, and its low humidity proton-conducting is good.In addition, compare embodiment 11, size changing rate is up to 30%.Tem observation can confirm to have the phase separation structure that territory degree is 35 nanometers.

Embodiment 16

(thering is the synthesizing containing sulfonic prepolymer a10 of following formula (G15))

With reference to method described in embodiment 11, the synthetic prepolymer a10 containing sulfonic group (end group is hydroxyl) with following formula (G15), wherein except the sulfonic aromatics that contains that derives from embodiment 2 with 64.7 grams (93 mmoles) replaces the sulfonic aromatics that contains that derives from embodiment 1.Prepolymer a10 has 16000 number-average molecular weight.

(chemical formula 44)

(prepolymer a10 as containing sulfonic segment (B1), prepolymer a1 as not stretching synthetic as the segmented copolymer b6 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

With reference to method described in embodiment 11, synthetic segmented copolymer b6, wherein replaces the prepolymer a12 containing sulfonic group (end group is as hydroxyl) take the prepolymer a10 containing sulfonic group (end group is as hydroxyl) of 16 grams (1 mmoles)., segmented copolymer b6 has 220000 weight-average molecular weight.

Configuration segmented copolymer b6 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, this film contains 100 % by mole of component units with formula (S1).The loading capacity that this film is obtained by neutralization titration is 24 meq/ gram, and identification does not have ketal group residual.This film is the self-support film that has toughness, estimates transparent, even.The proton conductivity of this film is 700 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 15 mS/cm, and its low humidity proton-conducting is good.In addition, size changing rate is low to moderate 20%.And the hot water resistance of this film is also good.

Tem observation can confirm to have the phase separation structure that territory degree is 30 nanometers.Contain sulfonic territory and all do not form external phase containing sulfonic territory.

Comparative example 2

Use commercially available Nafion (registered trademark) NRE211CS film (by Du Pont manufacturing) to assess various character.The loading capacity that this film is obtained by neutralization titration is 09 meq/ gram.This film range estimation is transparent and uniform film,

Tem observation fails to confirm to have a clear and definite phase separation structure.The proton conductivity of this film is 100 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 3 mS/cm.By thin film dipped, in hot water time, it expands tempestuously and is difficult to and processes, and in the time picking up film, breaks in some situation.

Comparative example 3

(not synthesizing containing the polyetherketone prepolymer c1 of sulfonic group and ketal group)

With reference to method described in embodiment 5, except the K-DHBP that the DHBP with 21 4 grams (100 mmoles) replaces 25.8 grams (100 mmoles), attempt synthetic not containing sulfonic polyetherketone prepolymer.From polymerization initial period, there is prepolymer precipitation, and be difficult to polymerization.Because this prepolymer is insoluble in solvent, the polymerization difficulty of segmented copolymer, therefore predict that this prepolymer cannot serve as electrolytic thin-membrane.Comparative example 4

According to Journal ofPolymer Science APolymer Chemistry, 48,2757, the synthesizing polyether of method described in 2010 sulfone segmented copolymer.First by 4,4 '-DCBP base sulfone reacts in oleum, and reaction finishes rear use sodium-chlor and saltouts and obtain 3,3 '-sodium disulfonate-4,4 '-DCBP base sulfone (hereinafter referred to as " SDCDPS ").Then under nitrogen atmosphere environment, in the single neck eggplant shape flask that is equipped with Dean-Stark separator tube, add 4 of the SDCDPS of 3.16 grams (6.0 mmoles), 1.34 grams (7.2 mmoles), 4 '-'-biphenyl diphenol, 1.49 grams of (10.8 mmole) salt of wormwood, 23 milliliters of NMP, 20 milliliters of toluene, remain on 1 50 ℃/2 hours azeotropic band water by system temperature.Then temperature is risen to 180 ℃, carry out reaction in 16 hours.After cooling, reaction soln is poured into water, and adds Repone K.To precipitate by filtered and recycled, under low pressure dry and obtain two ends and all have the hydrophilicity prepolymer of OH base in 60 ℃.

Then under nitrogen atmosphere environment, in the single neck eggplant shape flask that is equipped with Dean-Stark separator tube, add 4.31 grams of (15.0 mmoles) 4,4 '-DCBP base sulfone, 3 05 grams of (16 4 mmoles) 4,4 '-'-biphenyl diphenol, 3.39 grams of (24.5 mmole) salt of wormwood, 35 milliliters of NMP, 20 milliliters of toluene, remain on 150 ℃/2 hours azeotropic band water by system temperature.Then temperature is risen to 180 ℃, carry out reaction in 12 hours.After cooling, reaction soln is poured into water, by the sedimentation and filtration generating, further with washed with methanol.Precipitation is under low pressure dry and obtain two ends and all have the hydrophobicity prepolymer of OH base in 100 ℃.Under nitrogen atmosphere environment, in single neck eggplant shape flask that three-way cock is housed, add 0 45 grams of above-mentioned hydrophilicity prepolymers, 0.20 gram of above-mentioned hydrophobicity prepolymer, 55 milliliters of NMP, first by hydrophilicity prepolymer and hydrophobicity prepolymer 80 ℃ of dissolvings.After cooling under air atmosphere, add 0 02 grams of (0 06 mmole) decafluorobiphenyls, 0 01 grams of (0 07 mmole) salt of wormwood, then 120 ℃ of reactions 18 hours.After cooling, reaction soln is diluted with NMP, pours in Virahol, by generate sedimentation and filtration and clean with water.Then will generate polymkeric substance with acid treatment.To generate polymkeric substance in room temperature stirs after 2 days, by filtered and recycled polymkeric substance with 10 M aqueous sulfuric acids.This polymkeric substance is cleaned completely with pure water, be dried 10 hours and acquisition light brown polymkeric substance at 60 ℃.This polymkeric substance has 150000 weight-average molecular weight, is difficult to have high molecular weight.In addition, will generate polymkeric substance and in the vitriol oil, react 6 hours at 45 ℃, by the sulfonation of xenyl unit, clean completely with pure water.

The loading capacity that this film is obtained by neutralization titration is 27 meq/ gram.It is hard and crisp electrolytic thin-membrane, estimates opaque and inhomogeneous.The proton conductivity of this film is 200 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 01 mS/cm, compares with embodiment 1 to 4, and low humidity proton-conducting is poor.In addition, size changing rate L2/L1 is up to 150%, and the hot water resistance of this film is poor.

Comparative example 5

(thering is not the synthesizing containing sulfonic prepolymer c2 ' of following formula (G16))

With reference to method described in embodiment 14, the synthetic prepolymer c2 that does not contain sulfonic group (end group is hydroxyl), wherein add 33.6 grams of (100 mmoles) 2,2-bis-(4-hydroxy phenyl) HFC-236fa replaces 25.8 grams of (100 mmole) K-DHBP.Prepolymer c2 has 13000 number-average molecular weight.

With reference to method described in embodiment 12, the synthetic prepolymer c2 ' that does not contain sulfonic group (end group is fluorine) with following formula (G16), wherein adds the not prepolymer c2 (2 mmole) containing sulfonic group (end group is hydroxyl) to replace the prepolymer a1 containing sulfonic group (end group is hydroxyl).Prepolymer c2 ' has 14000 number-average molecular weight, and the value that is not 13400 containing the number-average molecular weight of the prepolymer c2 of sulfonic group, and both differences are due to linking agent (molecular weight is 630).

(chemical formula 45)

(thering is the synthesizing containing sulfonic prepolymer c3 of following formula (G17))

With reference to method described in embodiment 1, the synthetic prepolymer c3 containing sulfonic group (terminal hydroxyl groups) with following formula (G17), wherein add 33.6 grams of (100 mmoles) 2,2-bis-(4-hydroxy phenyl) HFC-236fa replaces 12.9 grams of (50 mmole) K-DHBP and 9.3 gram 4,4 '-'-biphenyl diphenol (Aldrich reagent, 50 mmoles).This prepolymer c3 has 19000 number-average molecular weight.

(chemical formula 46)

(segmented copolymer d1's is synthetic)

With reference to method described in embodiment 14, prepare segmented copolymer d1, wherein add the prepolymer c3 containing sulfonic group (end group is hydroxyl) of 19 grams (1 mmoles) to replace the prepolymer a2 containing sulfonic group (end group is hydroxyl), and replace the not prepolymer ar containing sulfonic group (end group is as fluorine) take the prepolymer c2' that does not contain sulfonic group (end group is as fluorine) of 14 grams (1 mmoles).This segmented copolymer d1 has 160000 weight-average molecular weight.

Configuration segmented copolymer d1 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, this film contains 0 % by mole of component units with formula (S1).The loading capacity that this film is obtained by neutralization titration is 23 meq/ gram, and by thin film dipped in hot water time, it expands violent and is difficult to process, and in the time picking up film, breaks in some situation.

Comparative example 6

(containing synthesizing of sulfonic prepolymer c4)

With reference to method described in embodiment 11, preparation is containing the prepolymer c4 of sulfonic group (end group is hydroxyl), the charging capacity containing sulfonic aromatics that wherein derives from embodiment 1 makes 8.93 grams (14.25 mmoles) into, what add that 34.1 grams (80.75 mmoles) derive from synthesis example 2 has 3 of a formula (H1), 3 '-disulfonic acid-4,4 '-difluorodiphenyl base ketone disodium, and make the charging capacity of K-DHBP into 25.8 grams (100 mmoles).This prepolymer c4 has 19000 number-average molecular weight.

(prepolymer c4 as containing sulfonic segment (B1), prepolymer a7 as not stretching synthetic as the segmented copolymer d2 of linking agent of phenyl containing sulfonic segment (B2), octafluoro connection)

With reference to method described in embodiment 11, prepare segmented copolymer d2, wherein replace the prepolymer a2 containing sulfonic group (end group is as hydroxyl) take the prepolymer c4 containing sulfonic group (end group is as hydroxyl) of 19 grams (1 mmoles), and replacing the prepolymer a1 ' containing sulfonic group (end group is as fluorine) take the prepolymer a7' that does not contain sulfonic group (end group is as fluorine) of 16 grams (1 mmoles), this segmented copolymer d2 has 180000 weight-average molecular weight.

Configuration segmented copolymer d2 is N-Methyl pyrrolidone (NMP) solution of 25 % by weight, prepares polymer electrolyte film with reference to method described in embodiment 11.

Containing in sulfonic component units, this film contains 15 % by mole of component units with formula (S1).The loading capacity that this film is obtained by neutralization titration is 15meq/ gram, and identification does not have ketal group residual.This film is the self-support film that has toughness, and estimates transparent, even.This film proton conductivity is 200mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 1mS/cm, poorer than the embodiment of segmented copolymer.On the other hand, size changing rate is low to moderate 5%, and the hot water resistance of this film is also good.

In addition, tem observation can confirm to have the common external phase isolating construction that territory degree is 22 nanometers.Contain sulfonic territory and all do not form external phase containing sulfonic territory.

Raw material for embodiment:

Purchased from Aladdin reagent (Shanghai) Co., Ltd. 4,4 '-difluorodiphenyl base ketone

(chemical formula 47)

Purchased from Aladdin reagent (Shanghai) Co., Ltd. 4,4 '-dichloro diphenylketone

(chemical formula 48)

Purchased from Aladdin reagent (Shanghai) Co., Ltd. 4,4 '-dibromo diphenylketone

(chemical formula 49)

Synthetic 4,4 '-bis-fluoro-3 of the method that discloses according to CN101717354A patent, 3 '-disulfonic acid benzophenone sodium salt:

(chemical formula 50)

Oleum (H ₂sO ₄/ SO ₃): the oleum take sulphur trioxide weight concentration as 20%, Chemical Reagent Co., Ltd., Sinopharm Group; Oleum take sulphur trioxide weight concentration as 50%, Chemical Reagent Co., Ltd., Sinopharm Group; Oleum take sulphur trioxide weight concentration as 65%, Aladdin reagent (Shanghai) Co., Ltd..

Organic solvent: dimethyl sulfoxide (DMSO) (DMSO), ethanol, methyl alcohol, acetone: Chemical Reagent Co., Ltd., Sinopharm Group.Alkali: sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus and ammoniacal liquor are all purchased from Chemical Reagent Co., Ltd., Sinopharm Group

The structure characterization methods of sulfonation reaction product in embodiment and comparative example:

Nucleus magnetic resonance (NMR)-hydrogen spectrum: ECX-400P JEOL, 400MHz, solvent d-DMSO.

Embodiment 17

1) by 4 of 22.9mmol, 4 '-difluoro benzophenone with containing 1261mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 175 ℃, under 015Mpa pressure, react 16 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium hydroxide be 70, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in ethanol, then be separated by filtration, 120 ℃ of vacuum-dryings obtain reaction product after 24 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 2: 1 ethanol and deionized water, confirm (as shown in Figure 2) through nuclear-magnetism, obtain 4 of purifying, 4 '-bis-fluoro-3,3 ', 5,5 '-tetrasulfonic acid benzophenone sodium salt.

Embodiment 18

(1) by 4 of 25mmol, 4 '-dichloro benzophenone with containing 150mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 65% oleum, in 200 ℃, under 0.9Mpa pressure, react 6 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium carbonate be 71, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in methyl alcohol, then be separated by filtration, 100 ℃ of vacuum-dryings obtain reaction product after 72 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 3: 1 ethanol and deionized water, confirm through nuclear-magnetism, obtain the 4,4 '-bis-chloro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sodium salt.

Embodiment 19

(1) by 4 of 26.7mmol, 4 '-dibromo benzophenone with containing 260mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 165 ℃, under 0.7Mpa pressure, react 22 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium bicarbonate be 7.0, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in propyl alcohol, then be separated by filtration, 110 ℃ of vacuum-dryings obtain reaction product after 48 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 1: 1 ethanol and deionized water, confirm through nuclear-magnetism, obtain the 4,4 '-bis-bromo-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sodium salt.

Embodiment 20

(1) by 4 of 22.9mmol, 4 '-difluoro benzophenone with containing 190mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 200 ℃, under 16Mpa pressure, react 6 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with potassium hydroxide be 74, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in propyl alcohol, then be separated by filtration, 150 ℃ of vacuum-dryings obtain reaction product after 6 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 27: 1 ethanol and deionized water, confirm through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sylvite.

Embodiment 21

(1) by 4 of 45mmol, 4 '-difluoro benzophenone with containing 495mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 200 ℃, under 24Mpa pressure, react 6 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with salt of wormwood be 71, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in methyl alcohol, then be separated by filtration, 120 ℃ of vacuum-dryings obtain reaction product after 36 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 1: 1 methyl alcohol and deionized water, confirm through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sylvite.

Embodiment 22

(1) by 4 of 50mmol, 4 '-difluoro benzophenone with containing 1500mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 20% oleum, in 150 ℃, under 2.9Mpa pressure, react 24 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with saleratus be 7.0, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in methyl alcohol, then be separated by filtration, 120 ℃ of vacuum-dryings obtain reaction product after 20 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 32: 1 ethanol and deionized water, confirm (as shown in Figure 3) through nuclear-magnetism, obtain 4 of purifying, 4 '-bis-fluoro-3,3 ', 5,5 '-tetrasulfonic acid benzophenone sylvite.

Embodiment 23

(1) by 4 of 25mmol, 4 '-difluoro benzophenone with containing 140mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 250 ℃, under 2 0Mpa pressure, react 1 hour; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium hydroxide be 70, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in methyl alcohol, then be separated by filtration, 120 ℃ of vacuum-dryings obtain reaction product after 16 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 21: 1 ethanol and deionized water, confirm through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sodium salt.

Embodiment 24

(1) by 4 of 25mmol, 4 '-difluoro benzophenone with containing 275mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 175 ℃, under 0 4Mpa pressure, react 16 hours; Reaction finish after, product is poured in deionized water, and with ammonia neutralization to PH be 73, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in acetone, then be separated by filtration, 120 ℃ of vacuum-dryings obtain reaction product after 24 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 25: 1 ethanol and deionized water, confirm through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone ammonium salt.

Embodiment 25

(1) 4,4 '-bis-fluoro-3 by 25mmol, 3 '-disulfonic acid benzophenone sodium salt with containing 50mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 200 ℃, under 1.3Mpa pressure, react 12 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium hydroxide be 7.1, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(3) reaction product obtaining is carried out in deionized water to recrystallization, confirm (as shown in Figure 4) through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sodium salt.

Embodiment 26

(1) by 4 of 25mmol, 4 '-difluoro benzophenone with containing 200mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 65% oleum, in 120 ℃, under 3Mpa pressure, react 48 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium hydroxide be 7.1, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in acetone, then be separated by filtration, 110 ℃ of vacuum-dryings obtain reaction product after 20 hours;

(3) reaction product obtaining is carried out in deionized water to recrystallization, confirm through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3,3 ', 5 of purifying, 5 '-tetrasulfonic acid benzophenone sodium salt.

Embodiment 27

(1), by 4,4 '-dichloro diphenylketone (25 mmole), sulphur trioxide concentration are that the oleum of 65 % by weight (contains 80 of 137.5 mmoles ₃) be placed in reactor, at 200 ℃, under 12 MPa, react 6 hours.Reaction finishes reaction mixture to pour in deionized water, then neutralizes until its pH value reaches 7.1 with sodium carbonate, then mixture solution evaporation is obtained to crude product.

(2) crude product that will derive from step (1) is fully dissolved in DMSO, by insoluble matter by centrifugation.The DMSO solution of reaction product is precipitated in methyl alcohol, and 100 ℃ of vacuum filtrations and dry last 72 hours and obtain and generate product.

(3) will derive from the product of step (2) recrystallize in the mixture of ethanol and deionized water (volume ratio is 3: 1), and obtain purifying 4,4 '-bis-chloro-3,3 ', 5,5 '-tetrasulfonic acid diphenylketone, four sodium, measure its structure by NMR.

Comparative example 7

(1) by 4 of 25mmol, 4 '-difluoro benzophenone with containing 800mmol sulphur trioxide be placed in there-necked flask take sulphur trioxide weight concentration as 50% oleum, in 200 ℃, under normal pressure, react 6 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium hydroxide be 7.1, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(2) gained crude product in step (1) is fully dissolved in dimethyl sulfoxide (DMSO), remove insolubles through centrifugation; The dimethyl sulphoxide solution of obtained reaction product is precipitated in ethanol, then be separated by filtration, 120 ℃ of vacuum-dryings obtain reaction product after 12 hours;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 2: 1 ethanol and deionized water, confirm (as shown in Figure 4) through nuclear-magnetism, obtain the 4,4 '-bis-fluoro-3 of purifying, 3 '-disulfonic acid benzophenone sodium salt.

Comparative example 8

(1) by 4 of 25mmol, 4 '-difluoro benzophenone with containing 200mmol sulphur trioxide be placed in reactor take sulphur trioxide weight concentration as 50% oleum, in 260 ℃, under 0.5MPa, react 50 hours; After reaction finishes, product is poured in deionized water, and to be neutralized to PH with sodium hydroxide be 74, obtain reaction soln; By obtained reaction soln evaporate to dryness, obtain crude product;

(3) reaction product obtaining is carried out to recrystallization in volume ratio is the mixing solutions of 2: 1 ethanol and deionized water, separate out without crystal.Product is confirmed (as shown in Figure 5) through nuclear-magnetism, and non-4,4 '-bis-fluoro-3,3 '-disulfonic acid benzophenone sodium salt, is the not clear degradation production of concrete structure.

The product that relatively derives from embodiment 17-27 and comparative example 7-8 is known, according to the present invention under 120～250 ℃ of temperature of reaction, in enclosed system, carry out compressive reaction, oleum take aromatics and sulphur trioxide weight concentration as 20～65% is as raw material, can obtain the aromatics that many sulfonation replace, and then provide necessary monomer for acquisition has the more polyether-ether-ketone of highly sulfonated.

Embodiment 28

(have formula (G6) containing sulfonic group polymkeric substance)

Be equipped with agitator, in 500 milliliters of 3 mouthfuls of flasks of nitrogen conduit and Dean-Stark separator, add 3.9 grams of salt of wormwood, 5.2 grams derive from 2 of synthesis example 1, 2-bis-(4-hydroxy phenyl)-1, 3-dioxolane mixture, 1.3 gram 4, 4 '-difluorodiphenyl base ketone, 8.8 grams derive from the sulfonic aromatics that contains with formula (G2) of embodiment 17, and the 18-hat-6-ether of 3.6 grams, in 60 milliliters of dimethyl sulfoxide (DMSO) (DMSO)/40 milliliter toluene, be with water in 145 ℃, rear intensification removes toluene, at 160 ℃, carry out 14 hours polyreactions.There is the precursor polymer of ketal group with acquisition with a large amount of water precipitations, purifying.This polymkeric substance has 195000 weight-average molecular weight.

N-Methyl pyrrolidone (NMP) solution that this polymkeric substance is configured to 25 % by weight, curtain coating is coated on glass substrate, and by its 100 ℃ dry 4 hours, 150 ℃ of thermal treatment 30 minutes under nitrogen atmosphere and obtain film.Splendid containing the solubleness of sulfonic group polymkeric substance before shaping.25 ℃ by thin film dipped in 10 % by weight aqueous sulfuric acid 24 hours to carry out proton exchange and protective reaction; then be impregnated in greatly excessive pure water 24 hours fully to clean film, obtain thus have formula (G6) containing sulfonic group polymer electrolyte film.

Containing in sulfonic component units, there is the component units with formula (S1) that contains 100 % by mole containing sulfonic group polymkeric substance of formula (G6).

The film thickness obtaining is 25 microns, and the loading capacity being obtained by neutralization titration is 4.2 meq/ gram, and identification does not have ketal group residual.This film is self-support film, estimates transparent, even.The proton conductivity of this film is 700 mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 1.5 mS/cm, and its low humidity proton-conducting is good.

Embodiment 29

(thering is not the synthesizing containing sulfonic prepolymer a1 ' of formula (G12))

With reference to the same procedure described in embodiment 11, obtain the not prepolymer a1 ' containing sulfonic group (end group is fluorine).This prepolymer has 11000 number-average molecular weight, and is not 10400 containing the number-average molecular weight of sulfonic prepolymer a1, and both differences are due to linking agent (molecular weight is 630).

(thering is the synthesizing containing sulfonic prepolymer a2 of formula (G13))

Be equipped with agitator, in 1000 milliliters of 3 mouthfuls of flasks of nitrogen conduit and Dean-Stark separator, add 41.5 grams of salt of wormwood (Aldrich reagent, 300 mmoles), 12 9 grams (50 mmoles) derive from the K-DHBP of synthesis example 1, 9.3 grams 4, 4 '-'-biphenyl diphenol (Aldrich reagent, 50 mmoles), 58 3 grams (93 mmole) derives from the sulfonic aromatics that contains of embodiment 17, and 49 1 grams of 18-hats-6 are (with light pure chemistry Industrial Co., Ltd product, 186 mmoles), with nitrogen replacement, then in 180 milliliters of dimethyl sulfoxide (DMSO) (DMSO) and 90 milliliters of toluene, be with water in 140 ℃, rear intensification is to remove toluene, 165 ℃ of polymerizations 12 hours.With a large amount of acetone precipitations, purifying, obtain the prepolymer a2 containing sulfonic group (end group is hydroxyl) with following formula (G13).This prepolymer has 15000 number-average molecular weight.

Obtain segmented copolymer b1 with reference to the same procedure described in embodiment 11.This segmented copolymer has 250000 weight-average molecular weight.

Use glass fibre filter by 25 % by weight N-N-methyl 2-pyrrolidone N-(NMP) the solution pressure filtrations of segmented copolymer b1, curtain coating is coated on glass substrate, and by its 100 ℃ dry 4 hours, lower 150 ℃ of thermal treatments of nitrogen atmosphere 10 minutes and obtain polyketals-one film (thick 25 microns).The solubleness of polymkeric substance is splendid.95 ℃ by thin film dipped in 10 % by weight aqueous sulfuric acid 24 hours with after carrying out proton exchange and protective reaction, then be impregnated in greatly excessive pure water 24 hours fully to clean film, obtain thus polymer electrolyte film.

Containing in sulfonic component units, the component units with formula (S1) that this film contains 100 % by mole.The loading capacity that this film is obtained by neutralization titration is 2.5 meq/ gram, and identification does not have ketal group residual.This film is the electrolytic thin-membrane that has toughness, estimates transparent, even.The proton conductivity of this film is 900mS/cm under 80 ℃, 85% relative humidity, under 80 ℃, 25% relative humidity, is 50 mS/cm, and its low humidity proton-conducting is good.In addition, this film dimensions velocity of variation is low to moderate 15%,, hot water resistance is also good.

In addition, tem observation can confirm that it has the common external phase isolating construction that territory degree is 25 nanometers.Contain sulfonic territory and all do not form external phase containing sulfonic territory.

(utilizing possibility) in industry

Polymer electrolyte of the present invention and polymer electrolyte film can be applicable to various electrochemical apparatus (such as fuel cell, water electrolysis equipment, chloric alkali electrolysis equipment etc.).In these equipment, it is suitable for fuel cell, particularly for being suitable for using the fuel cell of hydrogen as fuel.

In addition, the application of solid polymer type fuel battery of the present invention is also not particularly limited, and this solid polymer type fuel battery is preferably as the substitute of one-level battery and secondary battery in the past, as the power supply source of mancarried device and stationary power generation device, comprise mobile phone, Personal Computer, PDA, Kamera, digital camera etc.; Power equipment, comprises wireless dust collector etc.; Toy, moving body, comprises vehicle, for example electric bicycle, automobile, bus, truck; Ship and electric car; Or originate as the hybrid power supply of one-level battery or secondary battery in the past.

Description of reference numerals

M1: continuous structure

M2: sheet structure

M3: tubular structure

M4: island structure

Claims

1. containing sulfonic group polymkeric substance, it is characterized in that: comprise: contain sulfonic component units (A1) and do not contain sulfonic component units (A2), wherein, containing containing the identical or different component units with formula (S1) structure of counting 25 % by mole of above one or more by its integral molar quantity in sulfonic component units (A1):

(Chemical formula 1)

Having in the component units of formula (S1) structure, each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(wherein, R ¹for organic radical) ,-(CF ₂) _f-(integer that wherein, f is 1～5) or-C (CF ₃) ₂-in one; Each Z ¹be O or S independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; * be and there is the part of formula (S1) or the site that other component units is combined.

2. according to claim 1 containing sulfonic group polymkeric substance, it is characterized in that: this polymkeric substance has the repeating structure of one or more identical or different formulas (S2):

(Chemical formula 2)

Having in the repeating structure of formula (S2), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(wherein, R ¹for organic radical) ,-(CF ₂) _f-(integer that wherein, f is 1～5) or-C (CF ₃) _2-in one; And each Z ¹for independently 0 or S; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; Each Ar ¹independently for thering is following formula (q1) or divalent group (q2); * be and there is the part of formula (S2) or the site that other repeating structure is combined;

(chemical formula 3)

In formula (q1), X ²for ketone group, sulfuryl, direct key ,-PO (R ¹)-(, wherein R1 was organic radical) ,-(CF ₂) _f-(integer that wherein, f is 1～5) or-C (CF ₃) ₂in one; Having formula (q1) or group (q2) can be substituted.

3. according to claim 1 containing sulfonic group polymkeric substance, it is characterized in that: in formula (S1), X ¹for ketone group, Z ¹for O, all sulfonic groups are all at X ¹position between base.

4. according to claim 2 containing sulfonic group polymkeric substance, it is characterized in that: there is the repeating structure of formula (S2) for thering is the repeating structure of following formula (S3):

(chemical formula 4)

In formula (S3), each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently, * is and has the part of formula (S3) or the site that other repeating structure is combined.

According to described in any one in claim 1～4 containing sulfonic group polymkeric substance, it is characterized in that: one or more containing sulfonic segment (B1) and one or more not containing the segmented copolymers of sulfonic segment (B2) for containing.

6. according to claim 5 containing sulfonic group polymkeric substance, it is characterized in that: do not there is the repeating structure shown in following formula (P1) containing sulfonic segment (B2):

(chemical formula 5)

The position with (P1) can be optionally substituted, but not containing sulfonic group, X ³for electrophilic group, Z ³for electrophilic group, O or S, * is and has the part of formula (P1) or the site that other repeating structure is combined.

7. according to claim 6 containing sulfonic group polymkeric substance, it is characterized in that: there is the repeating structure of formula (P1) for thering is the repeating structure of following formula (P2):

(chemical formula 6)

* be and there is the part of formula (P2) or the site that other repeating structure is combined.

According to described in any one in claim 5～7 containing sulfonic group polymkeric substance, it is characterized in that: the connection base site of containing one or more connection segments.

9. contain the preparation method of sulfonic aromatics, it is characterized in that: comprise the step of being reacted with oleum by the aromatics of following general formula (M2) expression, wherein, temperature of reaction is 120 ℃～250 ℃, adopt enclosed system and react adding to depress, described in contain sulfonic aromatics structure as shown in general formula (M1):

(chemical formula 7)

In formula (M1) and (M2), each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(wherein, R ¹for organic radical) ,-(CF ₂) _f-(integer that wherein, f is 1～5) or-C (CF ₃) ₂in one; Each Y ¹be at least one in F, Cl, Br and I independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; M be 0 or 1, n be 0 or 1.

10. containing sulfonic aromatics, it is characterized in that: there is structure shown in following formula (M1), wherein, there is the content of the aromatics of structure shown in following formula (M2) below 5 % by weight,

(chemical formula 8)

Formula (M1) and (M2) in, each X ¹be ketone group, sulfuryl, direct key ,-PO (R independently ¹)-(wherein, R ¹for organic radical) ,-(CF ₂) _f-(integer that wherein, f is 1～5) or-C (CF ₃) ₂-in one; Each Y ¹be at least one in F, C1, Br and I independently; Each M ¹be the one in hydrogen, metallic cation, ammonium cation or the alkyl with 1～20 carbon atom independently; M be 0 or 1, n be 0 or 1.

11. is according to claim 10 containing sulfonic aromatics, it is characterized in that: in formula (M1), and X ¹for ketone group, Y ¹for F, all sulfonic groups are all at X ¹position between base.

12. polymer electrolytes, is characterized in that: comprise in claim 1～8 described in any one containing sulfonic group polymkeric substance.

13. polymer dielectric moldinies, is characterized in that: comprise the polymer electrolyte described in claim 12.

14. solid polymer type fuel battery, is characterized in that: right to use requires the polymer electrolyte described in 12.