JP2000082329A - Single ionic and proton conductive highpolymer substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive highpolymer substance having a high single ionic and/or proton conductivity which is stable over a wide temp. range and through a long period of service. SOLUTION: This conductive highpolymer substance is formed from a polymer having sulfate radical or sulfuric acid radical in each molecule and a polymer given by the expression-(R1-X)-, where R1 is organic residual radical with C ranging from 1 to 20 or an organic residual radical with C ranging from 1 to 20 and including hetero atoms such as N, O, S, F, Cl, Br, I, etc., X is N, O, S, or organic residual radical including these atoms, and (n) is an integer no less than 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a single ion and a proton conductive polymer used as an electrolyte of a device such as a secondary battery or a fuel cell, and more particularly, to an ion conducting polymer in a wide temperature range from a low temperature to a high temperature. And a single ion and proton conductive polymer capable of maintaining high proton conductivity for a long time.

[0002]

2. Description of the Related Art An ion conductive polymer used as a solid electrolyte for a secondary battery or a fuel cell is required to have high single ion conductivity. As a conventional ion conductive polymer, for example, a derivative of polyoxyethylene, polyoxypropylene, or a derivative thereof or a copolymer thereof, in which trifluoromethanesulfonate, perchlorate, or the like is dissolved as an electrolyte salt is used. And gel-like materials in which a solvent such as propylene carbonate is added thereto are known.

[0003] In polyoxyethylene or polyoxypropylene in these systems, the electrolyte salt is dissociated by ions due to a pseudo-solvation effect, and the dissociated ions move toward the electrode due to the segmental motion of the polyoxyethylene or the like. I do.

In this case, both the cation and the anion move toward the electrode in the ion. However, comparing these two, the cation moves more strongly than the cation which interacts with ether oxygen such as polyoxyethylene. However, there is no this kind of interaction, and therefore the anion having a relatively high degree of freedom has a higher ion transport number.

In general, in such a positive / negative ion (biion) conductor, when a voltage is applied across an active electrode (eg, a negative electrode / anode of a Li ion insertion type with respect to Li salt), an anion is formed. Migration is blocked by the anode, resulting in polarization. Since this kind of polarization causes a change in output of a battery or an electronic element or a decrease in driving potential, a cation-conductive polymer which does not cause migration of a counter anion is required. In this case, the polymer electrolyte containing no electrolyte salt can be an effective single ion conductor because one of the ionic groups is fixed to the polymer.

As a conventional single ion conductive polymer, for example, an ester type side chain terminal of polyacrylic acid is a sulfonic acid or an alkali metal salt of carboxylic acid, and a system in which this is mixed with polyoxyethylene, or A system in which the above side chain is oligooxyethylene is known, and a polymer expected to have a higher degree of ionic dissociation is a perfluorosulfonic acid polymer (Nafio).
n) or a perfluorocarboxylic acid polymer (Fl
emion) and the like are known.

On the other hand, conventional proton conductive polymers include, for example, polymer sulfonic acids such as polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and perfluorosulfonic acid, or polyacrylic acid and polymethacrylic acid. Acids, polymeric carboxylic acids such as perfluorocarboxylic acids, and cross-linked products thereof, and further,
A mixture of a polar polymer such as polyacrylamide, polyethyleneimine, and polyvinyl alcohol with an inorganic acid such as sulfuric acid, phosphoric acid, and hydrochloric acid, or a hydrated compound is known.

[0008]

However, according to these conductive polymers, for example, in the case of a conventional single ion conductive polymer, the terminal of the ester side chain is changed to an alkali metal salt of sulfonic acid or carboxylic acid. In the former case, the ionic conductivity is only 10 ⁻⁷ Scm ⁻¹ .
This is because the dissociation degree of sulfonic acid or carboxylic acid is low, and only two orders of magnitude smaller than that of the biionic conductor can be obtained.

Further, in the case of the latter perfluoro-based sulfonic acid or carboxylic acid polymer, its ionic conductivity is about 5 × 10 ⁻⁷ Scm ⁻¹ , although it is improved over the former. It is not enough for practical ionic conductivity. This is presumed to be due to the fact that the perfluorocarbon portion which controls the film-forming properties occupies a large proportion, so that the carrier density decreases and the conduction path is limited.

On the other hand, according to the conventional proton conductive polymer, for example, in the case of a polymer sulfonic acid or a polymer carboxylic acid, the degree of proton dissociation by the sulfonic acid and the carboxylic acid is low and the degree of dissociation is relatively high. Even in the case of fluorosulfonic acid, the molecular weight (equivalent weight) for introducing one sulfonic acid group is 1,100, and the introduction rate of sulfonic acid remains at a low level, so that high proton conductivity is obtained. It is difficult to secure.

For a water-containing system, evaporation at a high temperature and freezing at a low temperature are unavoidable due to the phase separation structure, and therefore, the state of water is always unstable. The physical properties of the molecular film are reduced, and particularly, the conductivity is gradually reduced at a high temperature. Similarly, the system is unstable when mixed with an acid such as sulfuric acid.

For example, as disclosed in JP-A-9-87369 and JP-A-9-87510, a sulfonic acid group or a sulfonic acid group is added to a heat-resistant aromatic polymer such as poly-P-phenylene and polyetheretherketone. Attempts have been made to introduce a phosphate group, but the degree of proton dissociation between the sulfonic acid group and the phosphate group is not high, and it is also difficult to ensure high proton conductivity in these cases.

Accordingly, an object of the present invention is to provide a conductive polymer having a high single ion conductivity or a high proton conductivity.
An object of the present invention is to provide a conductive polymer having stable single ion or proton conductivity in a wide temperature range and for a long time.

[0014]

According to the present invention, there is provided a polymer having a sulfate group in a molecule thereof.
General formula-(R ₁ -X) n- (wherein, R ₁ represents ₁ to 2
0 organic residues, or N, O, P, S, F, Cl, B
C containing a hetero atom such as r or I represents an organic residue of 1 to 20, X represents N, O, S or an organic residue containing these atoms, and n represents an integer of 2 or more. And a polymer represented by (1).

In order to achieve the above-mentioned object, the present invention provides a polymer having a sulfuric acid group in the molecule, and a compound represented by the general formula:
(R ₁ -X) n- (wherein, R ₁ is an organic residue having 1 to 20 carbon atoms or a carbon atom containing a heteroatom such as N, O, P, S, F, Cl, Br, or I) 1 to 20 organic residues;
Represents an organic residue containing N, O, S or an atom thereof, and n represents an integer of 2 or more). To provide.

The present invention uses a sulfate group or a polymer into which a large number of sulfate groups are introduced, has an electron-donating group such as N, O, or S in a main chain skeleton and has a high affinity for ions. In addition, the use of a polymer having the above-mentioned general formula having a low glass transition temperature and the combination of these polymers have specificity. At least up to now, in the use of single ion or proton conductive polymer, There is no example in which this combination is applied.

Sulfate groups or sulfate groups are characterized by high ionic dissociation properties. As a polymer capable of introducing these sulfate groups or sulfate groups into the molecule,
For example, any polymer containing a hydroxyl group is applicable. It is easy to substitute the hydroxyl group of these polymers with a sulfate group or a sulfate group, and there is no particular difficulty.

Examples of the polymer used as a precursor for obtaining a polymer having a sulfate group or a sulfate group (hereinafter referred to as a precursor polymer) include, for example, polyvinyl alcohol, polyallyl alcohol, and polypropyl alcohol. Examples include high molecular weight aromatic alcohols such as molecular aliphatic alcohols, polyphenols, polystyryl alcohols, and polyhydroxymethylphenylene oxide, and polysaccharides such as dextran, pullulan, cellulose, and hyaluronic acid.

Although the degree of polymerization of the precursor polymer is not particularly limited, in many cases, the range of 5 to 100,000 is set as the degree of polymerization, and more preferably, the range of 10 to 10,000 is more preferable. Is set. In the case of the latter range, if the value is below the lower limit, the mechanical strength and the film-forming property will decrease, and if the value exceeds the upper limit, the solubility will decrease.

For example, a sulfate group or a sulfate group is introduced into the precursor polymer as follows. That is, sulfur trioxide complexes of Lewis bases such as ethers, amines and sulfides, for example, pyridine / sulfur trioxide complex, dioxane / sulfur trioxide complex, N, N'-dimethylformamide / sulfur trioxide complex, triethylamine / trioxide A sulfurating agent such as a sulfur complex, a trimethylamine / sulfur trioxide complex, or an N-ethylmorpholine complex may be added in the absence or presence of a solvent, for example, at a reaction temperature of 0 to 150 ° C. and a reaction time of 1 to 20 hours. First, it reacts with the precursor polymer.

More specifically, the sulfation reaction is carried out using a hydrocarbon solvent such as n-hexane, an ether solvent such as tetrahydrofuran and dioxane, an amide solvent such as dimethylacetamide and dimethylformamide, and the like. In the presence or absence of various solvents such as dimethylsulfoxide, pyridine and the like. The reaction temperature is -200 to 2
00 ° C, more preferably -10 to 100 ° C,
The reaction time is set to 0.1 to 1000 hours. A more preferred reaction time is 1 to 20 hours. As a specific form of the sulfation reaction, it is possible to form a precursor polymer into a film before the reaction and to sulfate the film.

The amount of the sulfate group or sulfate group contained in the sulfated polymer thus obtained is often 0.05 to 5, preferably 0.1 to 5, per unit constituting the polymer. 3 or 2. If it is less than 0.05, the ionic or proton conductivity will be low. On the other hand, if it exceeds 5, the adhesion to substrates, electrodes, etc. will be poor, which is not preferable.

Next, the general formula-(R ₁ -X) n- (hereinafter, simply referred to as a general formula) will be described. R ₁ is 1 to
All organic residues having a C of 20 are applicable thereto, and these are N, O, P,
It may contain a hetero atom such as S, F, Cl, Br, I and the like. Specifically, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, fluoromethylene group, fluoroethylene group, fluoroethylene Propylene group, fluorobutylene group, fluoropentylene group, fluorohexylene group, fluoroheptylene group, fluorooctylene group, fluorononylene group, fluorodecylene group, fluoroundecylene group, fluorododecylene group, chloromethylene Group, chloroethylene group, chloropropylene group, chlorobutylene group, chloropentylene group, chlorohexylene group,
Chloroheptylene group, chlorooctylene group, chlorononylene group, chlorodecylene group, chloroundecylene group, chlorododecylene group, bromomethylene group, bromoethylene group, bromopropylene group, bromobutylene group, bromopentylene group, bromohexylene group, bromoheptylene group, Bromooctylene group, bromononylene group, bromodecylene group, bromoundecylene group, bromododecylene group, iodomethylene group, iodoethylene group, iodopropylene group, iodobutylene group, iodopentylene group, iodohexylene group, iodoheptylene group, iodooctylene Group, iodononylene, iododecylene, iodoundecylene, iodododecylene, perfluoromethylene, perfluoroethylene, perfluoropropylene, perfluoro Butylene group, perfluoropentylene group, perfluorohexylene group, perfluoroheptylene group, perfluorooctylene group, perfluorononylene group, perfluorodecylene group, perfluoroundecylene group, perfluorododecylene Group, perchloromethylene group, perchloroethylene group, perchloropropylene group, perchlorobutylene group, perchloropentylene group, perchlorohexylene group, perchloroheptylene group, perchlorooctylene group, perchlorononi Len group,
Perchlorodecylene group, perchloroundecylene group, perchlorododecylene group, perbromomethylene group, perbromoethylene group, perbromopropylene group, perbromobutylene group, perbromopentylene group, perbromohexylene group, Perbromoheptylene group, perbromooctylene group, perbromononylene group, perbromodecylene group, perbromoundecylene group, perbromododecylene group, periodmethylene group, periodethylene group, periodopropylene Group, periodobutylene group, periodopentylene group, periodohexylene group, periodoheptylene group, periodooctylene group, periodononylene group, periododecylene group, periodoundecylene group, par Iodododecylene group, phenylene group, toluylene group, xylyl Group, biphenylene group, naphthyl group, fluorophenylene group, fluorotoluylene group, fluoroxylylene group, fluorobiphenylene group, fluoronaphthyl group, chlorophenylene group, chlorotoluylene group, chloroxylylene group, chlorobiphenylene group, chloronaphthyl group , Bromophenylene group, bromotoluylene group, bromoxylylene group, bromobiphenylene group, bromonaphthyl group, iodophenylene group, iodotoluylene group, iodoxylylene group, iodobiphenylene group, iodonaphthyl group, perfluorophenylene group, perfluorotoluylene Group, perfluoroxylylene group, perfluorobiphenylene group, perfluoronaphthyl group, perchlorophenylene group, perchlorotoluylene group, perchloroxylylene group, perchlorobiphenyl group Group, perchloronaphthyl group, perbromophenylene group, perbromotoluylene group, perbromoxylylene group, perbromobiphenylene group, perbromonaphthyl group, periodophenylene group, periodo tolylene group, periodoxylylene R ₁ may be a group such as a periodic biphenylene group or a periodic naphthyl group. Methylene, ethylene and propylene groups are particularly preferred.

The polymer represented by the general formula may be used alone or as a mixture of two or more kinds, and may be used in combination with a polymer containing a sulfate group or a sulfate group (hereinafter, referred to as a sulfate group-containing polymer). The mixing ratio is 95/5 to 5% by weight.
It should be set to the range of 5/95, and when the number of the sulfate group-containing polymers is less than 5, it becomes difficult to obtain sufficient ion conductivity or proton conductivity. In many cases, these mixing ratios are set to a weight ratio of 90/10 to 20/80, more preferably 80/20 to 30/80, in the relation of “sulfuric acid group-containing polymer / polymer of the general formula”. The weight ratio is set to 70.

The conductive polymer of the present invention may be mixed with an organic polar solvent such as propylene carbonate, ethylene carbonate, acetonitrile, dimethylacetamide, dimethylformamide, or sulfuric acid, phosphoric acid, water, or the like. As means for obtaining a film from the conductive polymer of the present invention, for example, after dissolving a sulfuric acid group-containing polymer and a polymer of the general formula in a common solvent and mixing them, this is cast into a film. A method of molding, or a method of mixing both components and then applying pressure to the mixture, and the like, can be considered.

As another method, a precursor polymer is used in place of the sulfate group-containing polymer, and the precursor polymer and the polymer of the general formula are mixed in a common solvent and then cast. There is also a method in which a film is formed into a film, and a sulfated chemical is allowed to act on the film to sulfate the precursor polymer component, thereby obtaining a predetermined conductive polymer.

As the common solvent used in these methods, for example, aliphatic alcohol solvents such as methanol, ethanol, and propanol; amide solvents such as dimethylacetamide and dimethylformamide; and dimethyl sulfoxide and the like are used. Is done.

[0028]

Next, an embodiment of a single ion and proton conductive polymer according to the present invention will be described.

Example 1 Polyglycidol having a molecular weight of 1,000 was used.
After 74 g was dissolved in 100 ml of dimethylformamide and cooled, 20 ml of a dimethylformamide solution in which 7.95 g of a pyridine / sulfur trioxide complex had been dissolved was added dropwise in an ice bath at 0 to 2 ° C. and under a nitrogen atmosphere. The progress of the reaction was confirmed by the cloudiness of the solution.

Next, after 5 hours from the end of the dropping, water 1
After neutralizing by adding 00 ml and a 1M aqueous solution of LiOH to remove salts, lyophilization was carried out.
1.1 g of 00% lithium polyglycidol sulfate (weight based on lithium monosulfate group: 161) was obtained.

Next, the thus obtained lithium polyglycidol sulfate was dissolved in dimethylformamide together with polyoxyethylene having a molecular weight of 1,000, and the solution was cast on a lithium electrode.
After drying at 0 ° C. for 24 hours, a predetermined film was obtained. The ratio of lithium polyglycidol sulfate to polyoxyethylene in the solution was set to be 1: 1 by weight.

[0031]

Example 2 0.1 g of dextran having a molecular weight of 2,000
Was dissolved in 50 ml of dimethylacetamide and cooled, and 15 ml of a dimethylacetamide solution in which 1.47 g of a dioxane / sulfur trioxide complex was dissolved was added dropwise thereto in an ice bath (0 to 2 ° C.) and a nitrogen atmosphere. . 10 hours after the end of the dropping, 100 m of water
and dextran sodium sulfate having a degree of sulfation of 98% (weight based on sodium sulfate group: 14%).
1) 1.6 g was obtained.

Next, this dextran sulfate and polyoxypropylene having a molecular weight of 725 were dissolved in dimethylformamide at a weight ratio of 1: 1 and the resulting solution was cast on a platinum electrode. This was dried at 70 ° C. for 24 hours to obtain a predetermined film.

[0033]

Example 3 0.44 g of polyvinyl alcohol having a molecular weight of 88,000 was dissolved in 60 ml of dimethylacetamide dehydrated at 70 ° C. and cooled, and the solution was added to an ice bath (0 to 2 ° C.) and a nitrogen atmosphere. Then, 40 ml of dimethylacetamide in which 7.95 g of a pyridine / sulfur trioxide complex was dissolved was added dropwise. The solution became cloudy with the progress of the reaction.

Three hours after the completion of the dropwise addition, water 1
The solution was neutralized by adding 00 ml and a 1M aqueous solution of LiOH to remove salts, followed by lyophilization to obtain 1.23 g of polyvinyl lithium sulfate having a sulfation degree of 87% (weight based on lithium monosulfate group: 131). .

Next, a weight ratio of 4: 1: 1 was set between the polyvinyl lithium sulfate obtained above and polyoxyethylene having a molecular weight of 600 and polypropylene carbonate. Based on this weight ratio, these three components were used. It was dissolved in methanol, the resulting solution was cast on a stainless steel electrode, and dried at 70 ° C. for 24 hours to obtain a predetermined film.

[0036]

Example 4 0.44 g of polyvinyl alcohol having a molecular weight of 88,000 was dissolved in 60 ml of dimethylacetamide dehydrated at 70 ° C., cooled, and added to an ice bath (0 to 2).
Dimethylacetamide 40 in which 7.95 g of dioxane / sulfur trioxide complex was dissolved in a nitrogen atmosphere.
ml was added dropwise. The liquid became cloudy with the progress of the reaction.

After 5 hours from the end of the dropping, water 10
0 ml and a 1M aqueous solution of NaOH were added to neutralize the solution, and the solution was acidified using a cation exchange resin, freeze-dried, and sulfated 84% polyvinyl sulfate (weight per sulfate group: 124) 1 .20 g were obtained. Next, the obtained polyvinyl sulfate and polyoxyethylene having a molecular weight of 400 are cast on a platinum electrode using an aqueous solution in which the weight ratio of the former 3: the latter 1 is dissolved, and dried at 60 ° C. for 24 hours. Thus, a predetermined film body was obtained.

[0038]

Example 5 1.0 g of polyethylene glycol having a molecular weight of 1,000 was dissolved in 50 ml of dimethylformamide, and 1.59 g of a dimethylformamide / sulfur trioxide complex was dissolved in an ice bath and under a nitrogen atmosphere. 20 ml of the dimethylformamide solution was added dropwise.

One hour after the completion of dropping, water 50
After adding chloroform and extracting with chloroform, removing chloroform and dissolving in 0.1 M NaOH aqueous solution to form a sodium salt form, and then using a cation exchange resin to form an acid form, followed by freeze-drying. As a result, 1.2 g of polyoxyethylene having both ends sulfated (weight per sulfate group: 581, degree of sulfation: 100%) was obtained.

Next, this sulfated polyoxyethylene was dissolved in dimethylformamide, and the obtained solution was cast on a platinum electrode and dried at 60 ° C. for 24 hours to obtain a predetermined film. .

[0041]

EXAMPLE 6 0.10 g of tributylammonium hyaluronate having a molecular weight of 150,000 was dissolved in 10 ml of dimethylformamide, and 50 ml of a dimethylformamide solution containing 0.13 g of sulfur trioxide pyridine complex was added thereto in an ice bath. It was dropped. 3 after dripping is completed
After a period of time, 10 ml of water and a 1 M aqueous NaOH solution were added for neutralization, and then the reaction solution was reprecipitated in ethanol saturated with anhydrous sodium acetate.

Next, this was centrifuged, and the solid recovered by this was dissolved in water and dialyzed.
The cation-exchange resin was converted into an acid form and freeze-dried to obtain 0.15 g of sulfated hyaluronic acid (weight per one sulfate group: 189) having a degree of sulfation of 100%.

Next, this sulfated hyaluronic acid and polythioethylene were dissolved in dimethyl sulfoxide in a weight ratio of the former to 2 and the latter to 1, and the resulting solution was cast on a platinum electrode. And then 24 hours at 60 ° C.
A predetermined film was obtained by drying for a time.

[0044]

Comparative Example Perfluorosulfonic acid polymer (weight per sulfonic acid group: 1,100) and molecular weight of 1,000
Is dissolved in dimethylformamide such that the weight ratio of the latter to the former is 2 and the latter is 1;
The obtained solution was cast on a platinum electrode, and then dried at 70 ° C. for 24 hours to obtain a predetermined film.

Table 1 shows the results of the characteristic tests performed on the films on the electrodes obtained in the above Examples and Comparative Examples.

[0046]

[Table 1]

The test was performed as follows. In each case, after the same type of electrode is stacked on the film formed on the electrode and the film is sandwiched, the film is sealed in a closed cell under an argon atmosphere in a dry box, and the film is formed. Ionic conductivity and proton conductivity were measured as controls. The measurement was performed using an impedance analyzer (HP419).
4A), at a frequency of 100 to 150 MHz, the absolute value of the impedance and the phase angle of the membrane are measured at a predetermined temperature (24 ° C. and 100 ° C.), and a complex impedance plot is created to determine the conductivity. Calculated.

In the case of Examples 1 to 3, 24 ° C. and 100 ° C.
The ionic conductivity at a temperature of 100 ° C. and the DC conductivity before and after energization at 24 ° C. for 30 hours were measured. On the other hand, in Examples 4 to 6 and Comparative Example, 24 ° C. and 100 ° C. And the proton conductivity when left for 1 hour at a temperature of 24 ° C. and 100 ° C. respectively in an atmosphere of a relative humidity of 80% were measured.

According to Table 1, in Examples 1 to 3,
10 at 24 ° C^-6-10^-4 Class ionic conduction
Degrees at 100 ° C.^-4-10^-3Kula
3 shows the ionic conductivity of the metal.

And

The conventional ionic conductivity 10 exemplified in
Compared to the ^-7 class, it shows a remarkable improvement,
It is recognized that the compound has stable ionic conductivity over a wide temperature range.

Furthermore, there is no difference between the DC conductivity before and after the test at 30 o'clock conduction, and the DC conductivity is excellent with respect to the passage of time. In the case of Examples 4 to 6, it is recognized that the proton conductivity at 24 ° C. is superior to that of the comparative example, and the proton conductivity is generally high at 100 ° C.

The reason why the characteristics of the examples are excellent is that, first, a high carrier density is secured by a sulfate group having a high degree of ion dissociation or a polymer into which a large number of sulfate groups have been introduced. It has an electron-donating group such as O and S in the main chain skeleton, and therefore has a high affinity for ions, so that a large number of conduction paths are secured in the molecule.

The reason why the conductive polymer according to the present invention exhibits stable characteristics in a wide temperature range and a long-time conductivity has an electron-donating group such as N, O and S in the main chain skeleton. And the low glass transition temperature.

For the above reasons, a conductive polymer having excellent performance in both ionic conductivity and proton conductivity is constituted. In particular, in terms of proton conductivity, high proton conductivity is obtained. Having a means that the water content is unnecessary,
Naturally, the evaporation and freezing due to the temperature change disappear, and the performance is stabilized.

[0054]

As described above, according to the single ion and proton conductive polymer of the present invention, a polymer having a sulfate group or a sulfate group in the molecule is represented by the general formula:
-(R ₁ -X) n- (wherein, R ₁ represents an organic residue having 1 to 20 carbon atoms or a C atom containing a hetero atom such as N, O, P, S, F, Cl, Br, or I) Represents an organic residue of 1 to 20,
X represents N, O, S, or an organic residue containing these atoms, and n represents an integer of 2 or more).

[0051]

For the reasons described above, it has high ionic conductivity and high proton conductivity, and can maintain stable conductivity over a wide temperature range and for a long time of use.

Continued on the front page (72) Inventor Kazuaki Fukushima Maison M103, 1-2-15 Takada, Toshima-ku, Tokyo (72) Inventor Toshihiko Nishiyama 5-7-1 Shiba, Minato-ku, Tokyo Inside NEC Corporation (72) Inventor: Manabu Harada 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor: Masaki Fujiwara 7-1-1 Shiba, Minato-ku, Tokyo Inside NEC Corporation (72 Inventor Junko Nishiyama 5-7-1 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Shinako Okada 5-7-1 Shiba 5-chome, Minato-ku, Tokyo F-term (Reference) 4J002 AB05W BC12W BE01W BE02W CC03W CH02X CH06X CH07W CN01X GQ00 GQ02

Claims (12)

[Claims] 1. A polymer having a sulfate group in a molecule and a compound represented by the general formula-(R ₁ -X) n- (wherein R ₁ is an organic residue having 1 to 20 C, or N, O, P , S, F, Cl, Br,
C containing a hetero atom such as I represents an organic residue of 1 to 20, X represents N, O, S or an organic residue containing these atoms, and n represents an integer of 2 or more.) And a polymer represented by the following formula: 2. The single ion conductive polymer according to claim 1, wherein said X is O or S. 3. The method according to claim 1, wherein said R ₁ is a methylene group, an ethylene group, or a propylene group.
Item 3. The single ion conductive polymer according to Item 2 or 2. 4. The polymer having a sulfate group in the molecule,
The single ion conductive polymer according to any one of claims 1 to 3, wherein the single ion conductive polymer is obtained from a precursor polymer having a degree of polymerization of 10 to 10,000. 5. The polymer having a sulfate group in the molecule,
5. The composition according to claim 1, wherein said resin occupies at least 5% of the total weight of the polymer of the general formula.
Item 14. The single ion-conductive polymer according to any one of Items [1] to [10]. 6. The polymer having a sulfate group in the molecule,
0.05 to 5 for 1 unit constituting the polymer
The single ion conductive polymer according to any one of claims 1 to 5, wherein the single ion conductive polymer has a plurality of sulfate groups. 7. A polymer having a sulfate group in the molecule, and a compound represented by the general formula:
 − (R₁-X) n- (wherein R₁ Is C with 1-20
Residues, or N, O, P, S, F, Cl, Br, I
Represents an organic residue having 1 to 20 including a hetero atom such as
And X is N, O, S, or an atom containing these atoms.
And n represents an integer of 2 or more).
Having high proton conductivity, comprising:
Molecular body. 8. The proton conductive polymer according to claim 7, wherein said X is O or S. 9. The method according to claim 7, wherein said R ₁ is a methylene group, an ethylene group or a propylene group.
Item 9. The proton conductive polymer according to item 8 or 8. 10. The polymer having a sulfate group in the molecule,
The proton conductive polymer according to any one of claims 7 to 9, wherein the proton conductive polymer is obtained from a precursor polymer having a degree of polymerization of 10 to 10,000. 11. The polymer having a sulfate group in the molecule,
8. The method according to claim 7, wherein the polymer occupies at least 5% of the total weight of the polymer of the general formula.
Item 10. The proton-conductive polymer according to any one of items 0. 12. The polymer having a sulfate group in the molecule,
0.05 to 5 for 1 unit constituting the polymer
The proton conductive polymer according to any one of claims 7 to 11, wherein the proton conductive polymer has two sulfate groups.