JP5580804B2 - Ionic polymer - Google Patents

Description

  The present invention relates to an ionic polymer useful as an electrolyte for a lithium secondary battery or an electrolyte for a fuel cell.

  Lithium ion secondary batteries are small and have high capacity, so they are used in rechargeable batteries for portable devices. However, in recent years, due to demands for reducing environmental impact, they are expected to be used for power storage and batteries for electric vehicles. ing.

  In particular, in electric vehicle applications that are expected to be deployed in the near future, higher capacity is required than ever. As the most effective method for achieving high capacity, the use of a metal lithium negative electrode has been studied. When metallic lithium is used as the negative electrode active material, a high electromotive force is obtained, which is lightweight and greatly contributes to high capacity. However, the lithium ion secondary battery uses an organic electrolyte solution in which an electrolyte salt is dissolved in an organic solvent, so there is a problem that lithium dendrite precipitates and grows due to charge and discharge, and when this reaches the positive electrode, an internal short circuit occurs. Happens.

  In order to make it possible to use a metallic lithium negative electrode, it is necessary to physically suppress the precipitation of lithium dendrite, and there is an expectation for solidification of the electrolyte. For this reason, studies have been made on an all-solid electrolyte containing no organic electrolyte, and PEO (polyethylene oxide) can be cited as an example. However, in polymer solid electrolytes such as PEO, the mobility of the polymer chain dominates ionic conduction, so the ionic conductivity at room temperature and low temperature is extremely low, and the output of the battery hardly appears below room temperature. There is a problem.

On the other hand, as a technique for achieving both “solidification of electrolyte” and “expression of high ionic conductivity”, an electrolyte in which a nonaqueous solvent is held in an ionic polymer has been studied.
Patent Document 1 below discloses a copolymer of a tetrafluoroethylene (TFE) unit and a perfluorosulfonimide unit and a method for producing the same. However, these perfluoro-based polymers are impractical because of their very high price and the fact that they contain TFE units that are easily reduced to metallic lithium.

  Patent Document 2 discloses an electrolyte comprising a homopolymer of a monomer having a sulfonimide group and a non-aqueous solvent. Since these polymers do not contain a repeating unit having an aliphatic hydrocarbon, they have a drawback of being dissolved when mixed with a non-aqueous solvent. In order to use such an electrolyte as a solid electrolyte, co-curing with an elastomer is required, and the manufacturing method thereof is very complicated.

  Patent Document 3 below discloses a polymer electrolyte for a fuel cell in which water is contained in a copolymer composed of a repeating unit having an aliphatic hydrocarbon and a repeating unit containing a sulfonic acid group. In this polymer electrolyte, the sulfonic acid group retains a large amount of water, and the retained water exhibits high ionic conductivity. However, sulfonic acid groups cannot easily hold a non-aqueous solvent, and there is a problem that the degree of ion dissociation in the non-aqueous solvent is low. Therefore, the ionic conductivity is insufficient for use as an electrolyte for a lithium ion battery using a nonaqueous solvent as an electrolyte.

US Pat. No. 5,463,005 Japanese translation of PCT publication No. 2003-525957 Japanese National Patent Publication No. 10-503788

  The problem to be solved by the present invention is to provide an ionic polymer that contributes to excellent ion conductivity as a constituent material of a solid electrolyte for a lithium ion secondary battery in view of the above-mentioned problems of the prior art. .

  In order to solve the problems associated with the above-described prior art polymer electrolytes and to satisfy the above-mentioned demands, the present inventors have conducted intensive studies on the molecular structure of ionic polymers and conducted experiments. An ionic polymer containing a repeating unit composed of an aliphatic hydrocarbon which is difficult to swell and a repeating unit having a sulfonimide group capable of dissociating lithium ions or protons does not dissolve in a non-aqueous solvent and has high ionic conductivity It has been found that this has contributed to the present invention, and the present invention has been completed.

That is, the present invention is as follows.
[1] An ionic polymer containing a repeating unit composed of an aliphatic hydrocarbon and a repeating unit having a sulfonimide group, wherein the sulfonimide group in the repeating unit having a sulfonimide group is represented by the following formula (1) ):
—SO ₂ N (M) SO ₂ R ¹ (1)
{Wherein R ¹ is a group selected from the group consisting of a fluorine atom, an alkyl group having 1 to 8 carbon atoms, and a fluoroalkyl group, and M is a proton or a lithium ion. } The said ionic polymer characterized by the above-mentioned.

｛式中、Ｒ^２、及びＲ^３は、水素又は炭素数１〜４のアルキル基である。｝で表される、前記［１］に記載のイオン性高分子。 [2] The repeating unit comprising the aliphatic hydrocarbon has the following formula (2):

{Wherein R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms. } The ionic polymer as described in [1] above.

｛式中、Ｒ^１、及びＭは、記式（１）において定義したものと同じであり、Ｒ^４〜Ｒ^７は、水素原子、フッ素原子、炭素数１〜４のフルオロアルキル基、及び炭素数１〜４のアルキル基から成る群から選ばれる基であり、Ｒ^８は、炭素数１〜４のフルオロアルキル基、炭素数１〜４のアルキル基、エーテル基を有する炭素数１〜４のフルオロアルキル基、及びエーテル基を有する炭素数１〜４のアルキル基から成る群から選ばれる基であり、そしてｍ、及びｎは、０〜４の整数である。｝で表される、前記［１］又は［２］に記載のイオン性高分子。 [3] The repeating unit having a sulfonimide group has the following formula (3):

{Wherein R ¹ and M are the same as defined in Formula (1), and R ^{4 to} R ⁷ are a hydrogen atom, a fluorine atom, a C 1-4 fluoroalkyl group, and carbon. R ⁸ is a group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, and R ⁸ has 1 to 4 carbon atoms having a fluoroalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an ether group. It is a group selected from the group consisting of a fluoroalkyl group and an alkyl group having 1 to 4 carbon atoms having an ether group, and m and n are integers of 0 to 4. } The ionic polymer as described in said [1] or [2] represented by these.

｛式中、Ｒ^１、及びＭは、記式（１）において定義したものと同じであり、そしてＲ^８、及びｎは、前記式（３）において定義したものと同じである。｝で表される、前記［３］に記載のイオン性高分子。 [4] The repeating unit having a sulfonimide group has the following formula (4):

{Wherein R ¹ and M are the same as defined in Formula (1), and R ⁸ and n are the same as defined in Formula (3) above. } The ionic polymer as described in said [3] represented by these.

  [5] The content of the repeating unit having a sulfonimide group represented by the formula (1) is 1 mol% or more and 100 mol% or less of the repeating unit composed of the aliphatic hydrocarbon represented by the formula (2). The ionic polymer according to any one of [2] to [4], wherein

  [6] The ionic polymer according to any one of [1] to [5], wherein the ion exchange capacity of the ionic polymer is 0.5 meq / g or more and 3.0 meq / g or less. molecule.

  [7] A polymer electrolyte containing the ionic polymer according to any one of [1] to [6] and a nonaqueous solvent or water.

｛式中、Ｒ^２、及びＲ^３は、水素又は炭素数１〜４のアルキル基である。｝で表される脂肪族炭化水素からなる繰り返し単位と、下記式（６）：

｛式中、Ｒ^４〜Ｒ^７は、水素原子、フッ素原子、炭素数１〜４のフルオロアルキル基、及び炭素数１〜４のアルキル基から成る群から選ばれる基であり、Ｒ^８は、炭素数１〜４のフルオロアルキル基、炭素数１〜４のアルキル基、エーテル基を有する炭素数１〜４のフルオロアルキル基、及びエーテル基を有する炭素数１〜４のアルキル基から成る群から選ばれる基であり、ｍ、及びｎは、０〜４の整数であり、そしてＸはハロゲン原子である。｝で表されるハロゲン化スルホニル基を有する繰り返し単位と、
からなる共重合体を、塩基性化合物存在下、下記式（７）：
Ｒ^１ＳＯ_２ＮＨ_２ ・・・（７）
｛式中、Ｒ^１は、フッ素原子、炭素数１〜８のアルキル基、及びフルオロアルキル基から成る群から選ばれる基である。｝で表されるスルホンアミド化合物と、接触させてスルホンイミド化する、及び
（ＩＩ）得られたスルホンイミドを酸洗浄する、
を含む、式（３）中、Ｍがプロトンである、前記［３］に記載のイオン性高分子の製造方法。 [8] The following steps:
(I) The following formula (5):

{Wherein R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms. } And a repeating unit consisting of an aliphatic hydrocarbon represented by the following formula (6):

^{Wherein, R 4 to R ⁷ is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 4 carbon atoms, and a group selected from the group consisting of alkyl group having 1 to 4 carbon atoms, ^{R 8} is From the group consisting of a fluoroalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms having an ether group, and an alkyl group having 1 to 4 carbon atoms having an ether group The selected groups, m and n are integers from 0 to 4 and X is a halogen atom. }, A repeating unit having a sulfonyl halide group represented by:
In the presence of a basic compound, a copolymer consisting of the following formula (7):
R ¹ SO ₂ NH ₂ (7)
{Wherein R ¹ is a group selected from the group consisting of a fluorine atom, an alkyl group having 1 to 8 carbon atoms, and a fluoroalkyl group. And a sulfonamide compound represented by the following formula: (II) acid-washing the obtained sulfonimide,
The method for producing an ionic polymer according to the above [3], wherein in formula (3), M is a proton.

  [9] The ionicity according to [3], further comprising a step of bringing the ionic polymer produced by the method of [8] into contact with a lithium compound, wherein M is a lithium ion in the formula (3). Polymer production method.

  Since the ionic polymer of the present invention can maintain a solid state even when a non-aqueous solvent or water is contained, it contributes to high ion conductivity for a lithium secondary battery or a polymer electrolyte for a fuel cell. It is suitable as an ionic polymer.

Hereinafter, the present invention will be described in detail.
The ionic polymer of the present invention is a copolymer containing at least a repeating unit composed of an aliphatic hydrocarbon and a repeating unit having a sulfonimide group. In the present invention, the ionic polymer refers to a polymer having an ionic structure that can be ionically dissociated in the polymer, that is, an ionic functional group. The ionic functional group of the ionic polymer of the present invention is a sulfonimide group having a proton or a lithium ion as a counter ion.

  The ionic polymer of the present invention is characterized by containing a repeating unit composed of an aliphatic hydrocarbon and a repeating unit having a sulfonimide group. Here, the repeating unit consisting of an aliphatic hydrocarbon is composed only of carbon atoms and hydrogen atoms, and does not substantially contain an ionic functional group. Therefore, it is difficult to swell with a non-aqueous solvent and / or water and does not dissolve. Therefore, the ionic polymer of the present invention can maintain a solid state even after containing a non-aqueous solvent and / or water.

  On the other hand, the repeating unit having a sulfonimide group represented by the above formula (1) has a high affinity with a non-aqueous solvent and / or water and has a property of being easily retained. Since the non-aqueous solvent and / or water is locally present in the vicinity of the sulfonimide group of the above formula (1), high ionic conductivity can be expressed even if the content of the non-aqueous solvent and / or water is small. it is conceivable that.

  Other than the repeating units composed of aliphatic hydrocarbons, the repeating units composed of fluoroalkyl groups are also difficult to swell by non-aqueous solvents and / or water and difficult to hold. However, repeating units made of aliphatic hydrocarbons are characterized by being cheaper and more resistant to reduction with a metallic lithium negative electrode than repeating units made of fluoroalkyl groups. Accordingly, the repeating unit responsible for insolubility in the ionic polymer non-aqueous solvent and / or water is preferably a repeating unit composed of an aliphatic hydrocarbon.

｛式中、Ｒ^２、及びＲ^３は、水素又は炭素数１〜４のアルキル基である。｝で表される。 In the present invention, the repeating unit comprising an aliphatic hydrocarbon is preferably the following formula (2):

{Wherein R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms. }.

In R ² and R ³ of the repeating unit composed of an aliphatic hydrocarbon represented by the above formula (2), “an alkyl group of a hydrocarbon having 1 to 4 carbon atoms” is a saturated hydrocarbon, a straight chain But it may be branched. Specific examples of R ² and R ³ include
-H -CH ₃
-CH ₂ CH ₃
- _{(CH 2) 2} CH ₃
-CH _{(CH 3) 2}
- _{(CH 2) 3} CH 3
-CH _{2 CH} (CH _{3) 2
-CH (CH 3) CH 2 CH} 3
-C _{(CH 3)} 3
Is mentioned.

The ionic polymer of the present invention contains a repeating unit composed of an aliphatic hydrocarbon represented by the above formula (2). As the repeating unit composed of the aliphatic hydrocarbon represented by the above formula (2), at least one kind needs to be contained in the ionic polymer, but two or more kinds are combined and contained in the ionic polymer. Also good. When two or more kinds are contained in the ionic polymer, for example, it is possible to contain both an ethylene unit (R ² , R ³ = H) and a propylene unit (R ² = H, R ³ = CH ₃ ). is there. The repeating units composed of aliphatic hydrocarbons are all difficult to swell with a non-aqueous solvent and / or water, and are difficult to retain a non-aqueous solvent, and the above effects can be maintained even when two or more types are combined. .

で表される脂肪族炭化水素からなる繰り返し単位の内、１種又は２種以上を組み合わせて含有させることが好ましい。 From the viewpoint of manufacturing technology, ionic polymers are

It is preferable to contain one or two or more of repeating units composed of aliphatic hydrocarbons represented by

で表される共重合体ユニットである。尚、２種以上を組み合わせて含有させる場合、共重合体の構成は、ランダム構造、ブロック構造、マルチブロック構造、グラディエント構造いずれの構造であってもよい。 The ionic polymer is more preferably

It is a copolymer unit represented by these. In the case where two or more kinds are contained in combination, the copolymer may have a random structure, a block structure, a multi-block structure, or a gradient structure.

The ionic polymer of the present invention has the following formula (1):
—SO ₂ N (M) SO ₂ R ¹ (1)
{In the formula, R ¹ is a fluorine atom, a fluoroalkyl group having 1 to 8 carbon atoms or an alkyl group, and M is a proton or a lithium ion}. It is characterized by that. As a result of the local presence of a nonaqueous solvent or water in the vicinity of the sulfonimide group represented by the formula (1), it is considered that high ionic conductivity can be expressed. The position of the sulfonimide group represented by the formula (1) in the ionic polymer is not particularly limited, but from the viewpoint of effective ion conductivity, the sulfonimide group represented by the formula (1) is an ion. It is preferably present in the side chain of the conductive polymer.

R ¹ of the sulfonimide group represented by the above formula (1) is a fluorine atom, a fluoroalkyl group having 1 to 8 carbon atoms or an alkyl group. Here, the C1-C8 fluoroalkyl group or alkyl group is represented by the following formula (8):
_{-C m F a H 2m + 1} -a ··· (8)
{In the formula, m is an integer of 1 to 8, and a is an integer of 0 to 17. } Is a saturated hydrocarbon group that may be substituted with a fluorine atom, and may be linear or branched.

R ¹ of the sulfonimide group represented by the above formula (8) is preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms from the viewpoint of ion conductivity. Examples of perfluoroalkyl groups include
-CF ₃
-CF ₂ CF ₃
- _{(CF 2) 2} CF ₃
-CF _{(CF 3) 2}
- _{(CF 2) 3} CF 3
-CF _{2 CF} (CF _{3) 2
-CF (CF 3) CF 2 CF} 3
- _{(CF 2)} 4 CF ₃
- _{(CF 2)} 5 CF ₃
- _{(CF 2)} 6 CF ₃
- _{(CF 2)} 7 CF ₃
However, it is not limited to these. From the viewpoint of manufacturing technology, R ¹ is
-CF ₃
-CF ₂ CF ₃
- _{(CF 2) 2} CF ₃
-CF _{(CF 3) 2}
- _{(CF 2) 3} CF 3
It is more preferable that

  M of the sulfonimide group represented by the above formula (1) represents a counter ion, and M is a proton or a lithium ion. If M is a proton, the ionic polymer of the present invention functions as a proton conductor and can be used as an electrolyte for a fuel cell. On the other hand, if M is lithium ion, it functions as a lithium ion conductor. It can be used as an electrolyte for a lithium ion battery.

  Although the structure of the repeating unit which has a sulfonimide group represented by the said Formula (1) is not specifically limited, A vinyl sulfonimide unit, an allyl sulfonimide unit, and a styrene sulfonimide unit are mentioned preferably. More preferable examples of the structure of the repeating unit having a sulfonimide group represented by the above formula (1) include a tylene sulfonimide unit.

｛式中、Ｒ^１、及びＭは、記式（１）において定義したものと同じであり、Ｒ^４〜Ｒ^７は、水素原子、フッ素原子、炭素数１〜４のフルオロアルキル基、及び炭素数１〜４のアルキル基から成る群から選ばれる基であり、Ｒ^８は、炭素数１〜４のフルオロアルキル基、炭素数１〜４のアルキル基、エーテル基を有する炭素数１〜４のフルオロアルキル基、及びエーテル基を有する炭素数１〜４のアルキル基から成る群から選ばれる基であり、ｍ、及びｎは、０〜４の整数である。｝で表される繰り返し単位であることが好ましく、下記一般式（４）：

｛式中、Ｒ^１、及びＭは、記式（１）において定義したものと同じであり、そしてＲ^８、及びｎは、前記式（３）において定義したものと同じである。｝で表される繰り返し単位であることがより好ましい。 As the styrene sulfonimide unit, the following general formula (3):

{Wherein R ¹ and M are the same as defined in Formula (1), and R ^{4 to} R ⁷ are a hydrogen atom, a fluorine atom, a C 1-4 fluoroalkyl group, and carbon. R ⁸ is a group selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, and R ⁸ has 1 to 4 carbon atoms having a fluoroalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and an ether group. It is a group selected from the group consisting of a fluoroalkyl group and an alkyl group having 1 to 4 carbon atoms having an ether group, and m and n are integers of 0 to 4. } Is preferably a repeating unit represented by the following general formula (4):

{Wherein R ¹ and M are the same as defined in Formula (1), and R ⁸ and n are the same as defined in Formula (3) above. } Is more preferable.

R ^{4 to} R ⁷ of the sulfonimide unit represented by the above formula (3) are a hydrogen atom, a fluorine atom, a C 1-4 fluoroalkyl group or an alkyl group. Here, the C1-C4 fluoroalkyl group or alkyl group is represented by the following formula (9):
_{-C m F a H 2m + 1} -a ··· (9)
{Wherein m is an integer of 1 to 4 and a is an integer of 0 to 9. } Is a saturated hydrocarbon group that may be substituted with a fluorine atom, and may be linear or branched.

As examples of R ^{4 to} R ⁷ of the sulfonimide unit represented by the above formula (5), from the viewpoint of production technology,
-H
-CH ₃
-CH ₂ CH ₃
-CH _{(CH 3) 2}
-C _{(CH 3)} 3
-F
-CF ₃
-CF ₂ CF ₃
-CF _{(CF 3) 2}
Are preferable, but not limited thereto.

R ⁸ of the sulfonimide unit represented by the above formula (3) or formula (4) is a fluoroalkyl group or alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group or alkyl having 1 to 4 carbon atoms having an ether group. It is a group. Here, the fluoroalkyl group or alkyl group having 1 to 4 carbon atoms is represented by the following formula (10):
_{-C m F a H 2m-a} - ··· (10)
{Wherein m is an integer from 1 to 4 and a is an integer from 0 to 8. } And may be linear or branched.

In R ^{8 of the} sulfonimide unit represented by the above formula (3) or formula (4), the C 1-4 fluoroalkyl group or alkyl group having an ether group is represented by the following formula (11):
_{-OC m F a H 2m-a} - ··· (11)
{Wherein m is an integer from 1 to 4 and a is an integer from 0 to 8. } And may be linear or branched.

Examples of R ⁸ in the formula (3) or sulfonimide units represented by the formula (4), from the viewpoint of the viewpoint and the ion conductivity of the manufacturing technology,
—CH ₂ —
—CH ₂ CH ₂ —
-CF _2-
-CF ₂ CF _2-
-OCH ₂ CH ₂ -
-OCF ₂ CF _2-
Are preferable, but not limited thereto.

The ionic polymer may contain a repeating unit having a structure other than the repeating unit composed of the aliphatic hydrocarbon and the repeating unit having a sulfonimide group represented by the above formula (1). In particular, the following formula (12):
-SO ₂ M ··· (12)
{Wherein M is a proton or a lithium ion. } May be contained in the ionic polymer due to restrictions on production and purification of the ionic polymer.

The content of the repeating unit having a sulfonic acid group represented by the above formula (12) is 60 mol% or less of the repeating unit having a sulfonimide group represented by the above formula (1). In view of the above, it is preferably 50 mol% or less, more preferably 40 mol% or less.
In addition, when the repeating unit which has a sulfonic acid group represented by the said Formula (12) is contained in an ionic polymer, the ion exchange capacity mentioned later is the sulfonic acid group represented by the said Formula (12). It includes the derived ion exchange capacity.

  Further, the ionic polymer of the present invention needs to contain a repeating unit having the aliphatic hydrocarbon and a repeating unit having a sulfonimide group represented by the above formula (1), You may contain the repeating unit which has a sulfonic acid group represented by the said Formula (12), and the repeating unit which has another structure. In particular, a styrene derivative, an acrylic derivative, an acrylamide derivative, acrylonitrile, or the like can be contained as necessary.

  The ionic polymer of the present invention preferably has an ion exchange capacity of 0.5 meq / g or more and 3.0 meq / g or less. If the ion exchange capacity is 0.5 meq / g or more, sufficient ion conductivity can be ensured, and if it is 3.0 meq / g or less, good when a non-aqueous solvent is contained. Can ensure a sufficient strength. The ion exchange capacity is more preferably 0.6 meq / g or more and 2.0 meq / g or less, and further preferably 0.6 meq / g or more and 1.8 meq / g or less.

The ion exchange capacity of the ionic polymer of the present invention is measured as follows.
For the ionic polymer whose counter ion is lithium ion, the ionic polymer is immersed in a 10% by mass sulfuric acid aqueous solution, and the counter ion of the ion exchange group in the ionic polymer is converted from lithium ion to proton. The ionic polymer having protons is immersed in a saturated NaCl aqueous solution at 25 ° C., and the aqueous solution is stirred for a sufficient time. Subsequently, the proton in the saturated NaCl aqueous solution is neutralized and titrated with a 0.01N sodium hydroxide aqueous solution. The ionic polymer obtained after neutralization in which the counter ion of the ion exchange group is in the form of sodium ion is rinsed with pure water, further vacuum-dried, and weighed. The amount of sodium hydroxide required for neutralization is M (mmol), and the mass of the ionic polymer whose ion-exchange group counter ion is sodium ion is W (mg).
EW = (W / M) −23 + 1 (when the counter ion is a proton), or EW = (W / M) −23 + 7 (when the counter ion is a lithium ion)
To obtain the equivalent mass EW (g / equivalent).

  Furthermore, the ion exchange capacity (milli equivalent / g) is calculated by taking the inverse of the obtained EW value and multiplying it by 1000. This ion exchange capacity is adjusted to fall within the above numerical range by adjusting the number of ion exchange groups present in 1 g of the ionic polymer.

The ionic polymer of the present invention is a copolymer containing a repeating unit comprising the aliphatic hydrocarbon and a repeating unit having a sulfonimide group represented by the above formula (1). The combined structure may be any of a random structure, a block structure, a multi-block structure, and a gradient structure.
The content rate of the repeating unit which has a sulfonimide group represented by the said Formula (1) is 1 mol% or more and 100 mol% or less of the repeating unit which consists of an aliphatic hydrocarbon represented by the said Formula (2). If the content is 1 mol% or more, sufficient ionic conductivity can be ensured, and if it is 50 mol% or less, sufficient strength can be ensured. The content is preferably 5 mol% or more and 80 mol% or less, and more preferably 5 mol% or more and 60 mol% or less.

The content of the repeating unit having a sulfonimide group represented by the formula (1) has an integral value of an arbitrary proton derived from a repeating unit composed of an aliphatic hydrocarbon and a sulfonimide group from ¹ H-NMR. It can be calculated from the integral value of any proton derived from the repeating unit.

  The ionic polymer of the present invention, after contacting with a sulfonamide compound in the presence of a basic compound using a copolymer consisting of a repeating unit consisting of an aliphatic hydrocarbon and a repeating unit having a sulfonyl halide group, Although it can manufacture by wash | cleaning and making it contact with a lithium compound as needed, the manufacturing method of the said copolymer is demonstrated first.

The above copolymer, that is, a copolymer comprising a repeating unit comprising an aliphatic hydrocarbon represented by the above formula (2) and a repeating unit having a sulfonyl halide represented by the above formula (6) is a styrene-based copolymer. A block copolymer obtained by hydrogenating a conjugated diene portion of a block copolymer of a conjugated diene compound and an aromatic vinyl compound, which are collectively referred to as an elastomer, is treated with a known sulfonation, chlorosulfonation, sulfonimidation, or the like. It can be obtained by introducing an imide group.
Examples of the block form include a diblock copolymer, a triblock copolymer, a radial block copolymer, a multiblock copolymer, and the like. Among these, a triblock copolymer is preferably used.

As the styrene-based elastomer, those obtained by block copolymerization of an aromatic vinyl compound and a conjugated diene compound by a known method such as anionic polymerization, cationic polymerization, coordination polymerization, radical polymerization and the like are used without limitation. These production conditions are not particularly limited, but those produced by living anionic polymerization are preferably used.
Specific examples of the styrenic elastomer include polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer (SEBS) and polystyrene-poly (ethylene-propylene) -polystyrene triblock (SEPS) from the viewpoint of production. Preferred examples include copolymers, polystyrene-polyisobutylene-polyethylene triblock copolymers (SIBS), and the like, but are not limited thereto.

Next, it is preferable to obtain the ionic polymer of the present invention using a copolymer comprising a repeating unit composed of an aliphatic hydrocarbon and a repeating unit having a sulfonyl halide group obtained by the above production method. A manufacturing method will be described.
Even if the method for introducing a sulfonimide group is a method of synthesizing a prepolymer having a site capable of introducing a sulfonimide group and then introducing a sulfonimide group into a site where the prepolymer can be introduced, A method of polymerizing a monomer having a group may also be used. Among these, the former method is more preferable from the viewpoint of work efficiency.

  Examples of the structure capable of introducing a sulfonimide group include a structure having a hydrogen atom directly bonded to an aromatic ring or a functional group that can be converted into a sulfonimide. When it has a hydrogen atom directly bonded to an aromatic ring, it can be converted into a sulfonimide group after introducing a sulfonic acid group into the aromatic ring by a sulfonation reaction. The functional group that can be converted into a sulfonimide group is not particularly limited, and examples thereof include allyl sulfonic acid, vinyl sulfonic acid, and styrene sulfonic acid.

  As the sulfonating agent used in the sulfonation reaction, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid and the like can be used, but are not limited to these acids. In the sulfonation reaction, the sulfonating agent and the prepolymer may be in contact with each other. The prepolymer may be in a solid state such as a powder or a membrane, or in a solution state dissolved in a solvent. The degree of sulfonation can be easily controlled by the amount of sulfonating agent used, the reaction temperature and the reaction time.

  The sulfonation reaction can be performed in a non-solvent, but a solvent may be used. Here, the solvent that can be used may be any solvent that is inert to the reactants. For example, hydrocarbon solvents such as pentane, hexane, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetra And halogenated hydrocarbon solvents such as chloroethane. In addition, these solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The reaction temperature for carrying out the sulfonation reaction is preferably -50 to 100 ° C, more preferably 0 to 50 ° C. Although reaction time changes with conditions, such as the kind of ionic polymer to be used, reaction temperature, a sulfonating agent, and a solvent, from a viewpoint of production efficiency, it is 0.1 to 100 hours, Preferably it is 1 to 48 hours.

In order to convert a sulfonic acid group into a sulfonimide group, first, the following formula (13):
-SO ₂ X ··· (13)
{Wherein X is a halogen atom. } Must be converted to a sulfonyl halide group represented by In the above formula (13), X is a halogen atom, but X is preferably fluorine, chlorine, bromine or iodine, more preferably fluorine or chlorine, from the viewpoint of handling properties or production.

As the halogenating agent for converting the sulfonic acid group to the SO ₂ Cl group, thionyl chloride, phosphorus pentachloride, phosphorus oxychloride and the like can be used, but are not limited to these halogenating agents. It is preferable to use thionyl chloride for reasons such as handling. In addition, these halogenating agents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The conditions for sulfonimidization of the precursor polymer are not particularly limited. As an example, in the presence of a basic compound in an aprotic solvent, the following formula (7):
R ¹ SO ₂ NH ₂ (7)
{Wherein R ¹ is the same as defined in the above formula (1). } Is contacted with a sulfonamide compound represented by the following formula (14):
—SO ₂ N (M ′) SO ₂ R ¹ (14)
{Wherein M ′ is a quaternary ammonium ion, an alkali metal, or an alkaline earth metal, and R ¹ is the same as defined in the above formula (1). } It is preferable to obtain an ionic polymer having a repeating unit having a sulfonimide group represented by In the sulfonimidation, the obtained ionic polymer may contain a sulfonic acid unit represented by the above formula (12) due to the influence of residual water in the reaction system. However, the sulfonic acid unit may be present in the ionic polymer. The molar content of the repeating unit having a sulfonimide group represented by the above formula (12) is 60 mol% or less of the repeating unit having a sulfonimide group represented by the above formula (1). From the viewpoint of property, it is preferably 50 mol% or less, more preferably 40 mol% or less.

Specific examples of the basic compound include carbonates such as Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , CaCO ₃ and BaCO ₃ , and bicarbonates such as NaHCO ₃ and KHCO _3. , Tertiary amines such as triethylamine and diisopropylethylamine, and heterocyclic amines such as pyridine and imidazole. Although not limited thereto, the basic compound is preferably a tertiary amine such as diisopropylethylamine.

  The solvent used in the sulfonimide reaction may be any solvent that is inert to the reactants, and is acetonitrile, tetrahydrofuran, diethyl ether, monoglyme, diglyme, triglyme, tetraglyme, dimethylformamide, dimethylacetamide, N- Examples include methylpyrrolidinone, dioxane, dimethyl sulfoxide, sulfolane, and the like. These solvents may be used alone or in combination of two or more.

  The reaction temperature when the sulfonimide reaction is performed is preferably 0 to 200 ° C, and more preferably 50 to 150 ° C. From the viewpoint of production efficiency, the reaction time is preferably 0.1 hour to 100 hours, and more preferably 1 hour to 48 hours.

The obtained polymer is washed with water, warm water and acid as necessary, and then immersed in a lithium hydroxide aqueous solution to form a sulfonimide lithium salt, whereby the above formula (1) and the above formula (2) are obtained. Can be obtained. In addition, since the unreacted SO ₂ Cl group can be changed to the SO ₃ Li group by performing hydrolysis treatment in a basic reaction liquid after washing with water, warm water and acid, this hydrolysis treatment is performed. It is also preferable to do this.

  The ionic polymer of the present invention can be used as a polymer electrolyte for a lithium ion battery by retaining at least a non-aqueous solvent. Moreover, it can be used as a polymer electrolyte for fuel cells by retaining water. Unlike the so-called “dry polymer electrolyte”, the “polyelectrolyte” may contain a nonaqueous solvent and / or water in the polymer, and may contain other lithium salt as necessary. . In the present specification, the “polyelectrolyte” refers to a complex of a polymer, a non-aqueous solvent, or other necessary additives.

  Examples of the non-aqueous solvent include aprotic solvents, and aprotic polar solvents are preferable. Specific examples of the non-aqueous solvent include, for example, cyclic carbonates represented by ethylene carbonate, propylene carbonate and the like, lactones represented by γ-butyrolactone, γ-valerolactone, and the like, and cyclic sulfones represented by sulfolane and the like. , Cyclic ethers represented by tetrahydrofuran, dioxane, etc., chain carbonates represented by methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, etc., nitriles represented by acetonitrile, propionitrile, etc., dimethyl ether, dimethoxyethane , Ethers typified by diethylene glycol dimethyl ether, triglyme, tetraglyme and the like, and chain carboxylic acid esters typified by methyl propionate.

  The non-aqueous solvent may be used alone or in combination of two or more, but particularly from the viewpoint of improving ionic conductivity, the non-aqueous solvent preferably contains one or more cyclic aprotic polar solvents, More preferably, it contains at least one cyclic carbonate. Moreover, it is preferable that a non-aqueous solvent is a mixed solvent of 2 or more types of solvents from a viewpoint of the improvement of ion conductivity. Examples of the non-aqueous solvent in this mixed solvent are the same as those described above.

The polymer electrolyte of the present invention preferably contains a lithium salt in addition to the ionic polymer described below. Here, the lithium salt is not particularly limited as long as it is used as a normal nonaqueous electrolyte, and any lithium salt may be used. As such a lithium salt, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiN (SO ₂ CF ₃ ) _{2 and the} like are preferably exemplified.

  These lithium salts can be used alone or in combination of two or more. The lithium salt can be contained at a concentration of preferably 0.01 to 3 mol / liter, more preferably 0.1 to 2 mol / liter, as the concentration in the non-aqueous solvent.

The measurement methods and evaluation methods for various physical properties used in the following examples and the like were as follows.
(1) Ion exchange capacity The ion exchange capacity of the ionic polymer was measured by the following method.
For the ionic polymer in which the counter ion is lithium ion, the ionic polymer was immersed in a 10% by mass sulfuric acid aqueous solution, and the counter ion of the ion exchange group in the ionic polymer was converted from lithium ion to proton. The proton-containing ionic polymer was immersed in 20 mL of a saturated NaCl aqueous solution at 25 ° C. and left for 30 minutes with stirring. Next, the protons in the saturated aqueous solution were neutralized and titrated with 0.01N aqueous sodium hydroxide solution using phenolphthalein as an indicator. The ionic polymer in which the counter ion of the ion exchange group obtained by filtration after neutralization was in the state of sodium ion was rinsed with pure water, further vacuum dried and weighed. The amount of sodium hydroxide required for neutralization is M (mmol), and the mass of the ionic polymer whose ion-exchange group counterion is sodium ion is W (mg).
EW = (W / M) −23 + 1 (when the counter ion is a proton)
EW = (W / M) −23 + 7 (when the counter ion is a lithium ion)
Thus, the equivalent mass EW (g / equivalent) of the ionic polymer was determined.
Furthermore, the ion exchange capacity (milli equivalent / g) was calculated by taking the inverse of the obtained EW value and multiplying it by 1000.

(2) Infrared spectroscopic analysis (IR)
The infrared spectroscopic analysis of the ionic polymer was measured using Spectrum One (manufactured by Perkin Elmer).

(3) Film thickness (μm)
The film thickness of the polymer electrolyte was measured using a Digimatic Thickness Gauge 547-401 manufactured by Mitutoyo Corporation in an argon glove box.

(4) Content of ionic polymer in polymer electrolyte (%)
The content of the ionic polymer in the polymer electrolyte is determined from the ratio between the weight of the ionic polymer after drying at 120 ° C. for 15 hours and the weight of the polymer electrolyte obtained using the ionic polymer. Asked.

(5) Ionic conductivity (S / cm)
A symmetric cell of Au / polymer electrolyte / Au was produced by sandwiching a polymer electrolyte in stainless steel vapor-deposited with Au and sealing with an aluminum laminate film in an argon glove box. Here, the Au electrode was 2 cm square and the electrode area was 4 cm ² . The produced symmetrical cell was measured for impedance in an isothermal atmosphere at 25 ° C. in the frequency range of 20 kHz to 0.1 Hz using an electrochemical measuring device (Solartron, 1280B), and the measured resistance value R ′ (Ω) From the following formula:
σ = L / (R ′ × A)
{Where σ is ionic conductivity (S / cm), L is the distance between electrodes (cm), R 'is the measured resistance (Ω), and A is the electrode area (cm ² ). }, Ion conductivity was calculated. The thickness of the polymer electrolyte was used as the distance between the electrodes.

[Example 1] Synthesis of ionic polymer (following formula (15)) and ionic conductivity

で表されるポリスチレンスルホン酸-block-ポリ(エチレン-ran-ブチレン)-block-ポリスチレンスルホン酸高分子の５％溶液（スチレン含有率２９重量％、Ａｌｄｒｉｃｈ社製、商品番号４４８８８５）を、高分子の含有量が９重量％になるようにエバポレーターで濃縮した。得られた溶液をシャーレに入れ、真空乾燥で溶媒を除去し、さらに８０℃で１時間真空乾燥し、その後シャーレから剥がすことにより、膜厚１３５μｍの高分子膜を作製した。得られたイオン性高分子のイオン交換容量は１．６２ミリ当量／ｇであった。イオン交換容量の結果より、［脂肪族炭化水素からなる繰り返し単位］：［スチレンからなる繰り返し単位］：［スルホン酸基を有する繰り返し単位］＝６．５：０．５：１のｍｏｌ比で存在していることが分かった。 (Production of ionic polymer membrane having sulfonic acid group)
Following formula (16):

A 5% solution of polystyrenesulfonic acid-block-poly (ethylene-ran-butylene) -block-polystyrenesulfonic acid polymer represented by the formula (styrene content 29% by weight, manufactured by Aldrich, product number 448885) is polymerized. The solution was concentrated with an evaporator so that the content of was 9% by weight. The obtained solution was put into a petri dish, the solvent was removed by vacuum drying, further vacuum-dried at 80 ° C. for 1 hour, and then peeled off from the petri dish to prepare a polymer film having a thickness of 135 μm. The ion exchange capacity of the obtained ionic polymer was 1.62 meq / g. From the result of ion exchange capacity, [Repeating unit consisting of aliphatic hydrocarbon]: [Repeating unit consisting of styrene]: [Repeating unit having sulfonic acid group] = 6.5: 0.5: 1 I found out that

(Synthesis of ionic polymer film having SO ₂ Cl group)
8 g of the polymer film obtained above was immersed in 400 mL of an N, N-dimethylformamide solution in which 140 g of thionyl chloride was dissolved at room temperature for 20 hours to convert sulfonic acid groups into SO ₂ Cl groups. After completion of the reaction, the obtained polymer film was washed with water until the washing solution became neutral, then further washed with ethanol, and vacuum-dried at 60 ° C. for 20 hours. Brown polymer film is obtained, and was ^measured, 1173Cm -1, confirmed the peak of _SO 2 Cl group to 1377 cm ^-1.

(Membrane synthesis of an ionic polymer having a sulfonimide group (SO ₂ NHSO ₂ CF ₃ ) (formula (15))
The obtained polymer film having SO ₂ Cl groups was immersed in 600 g of a diethylene glycol dimethyl ether solution in which CF ₃ SO ₂ NH ₂ was dissolved at 1.0 mol / kg and (i-Pr) ₂ EtN was dissolved at 1.5 mol / kg. The sulfonimide reaction was performed at 130 ° C. for 20 hours. Subsequently, the obtained polymer was washed with water, washed with a 10% by weight aqueous sulfuric acid solution, and then immersed in a 15% by weight aqueous potassium hydroxide solution at 90 ° C. for 2 hours to hydrolyze residual SO ₂ Cl groups. The obtained polymer film was washed with water, acid washed, washed with water, and then vacuum-dried at 120 ° C. for 20 hours to obtain an ionic polymer film having a film thickness of 135 μm whose counter ion is proton. When IR was measured, the disappearance of the SO ₂ Cl group peak and the peak of the sulfonimide group at 1321 cm ⁻¹ were confirmed. It was also confirmed by the side reaction that a small amount of sulfonic acid group was present. As a result of analysis, it was found that the conversion rate from SO ₂ Cl groups to sulfonimide groups was 89%. The ion exchange capacity of the obtained ionic polymer membrane was 1.35 meq / g. From the results of ion exchange capacity and IR analysis, [Repeating unit consisting of aliphatic hydrocarbon]: [Repeating unit consisting of styrene]: [Repeating unit having sulfonic acid group]: [Repeating unit having sulfonimide group] = 6 It was found to exist in a molar ratio of 5: 0.5: 0.1: 1.

(Ionic conductivity measurement of ionic polymer (15))
The vacuum-dried ionic polymer was cut into 4 cm square, and immersed in pure water for 24 hours at room temperature to contain water in the ionic polymer. Thereafter, the ionic polymer was taken out, and water remaining on the surface of the ionic polymer was wiped off with a filter paper and removed to obtain a polymer electrolyte having a film thickness of 250 μm. At a relative humidity of 50%, the content of the ionic polymer in the polymer electrolyte was 25% by weight, and the ionic conductivity was 2.1 × 10 ⁻² S / cm.

（スルホンイミド基（ＳＯ_２ＮＬｉＳＯ_２ＣＦ_３）を有するイオン性高分子膜の合成）
実施例１で得られた上記式（１５）で表される高分子を、１Ｎ水酸化リチウム水溶液に浸漬して、対イオンがリチウムイオンであるイオン性高分子膜を得た。得られたイオン性高分子膜のイオン交換容量を測定したところ、イオン交換容量は、１．３４ミリ当量／ｇであった。また、得られたイオン性高分子を１２０℃で１５時間真空乾燥し、膜厚を測定したところ、膜厚は１３５μｍであった。 [Example 2] Synthesis and ionic conductivity of ionic polymer (following formula (17))

(Synthesis of an ionic polymer film having a sulfonimide group (SO ₂ NLiSO ₂ CF ₃ ))
The polymer represented by the above formula (15) obtained in Example 1 was immersed in a 1N aqueous lithium hydroxide solution to obtain an ionic polymer film whose counter ion was lithium ion. When the ion exchange capacity of the obtained ionic polymer membrane was measured, the ion exchange capacity was 1.34 meq / g. Moreover, when the obtained ionic polymer was vacuum-dried at 120 degreeC for 15 hours and the film thickness was measured, the film thickness was 135 micrometers.

(Ionic conductivity of ionic polymer membrane (formula (17)))
The vacuum-dried ionic polymer is cut into 4 cm squares in an argon glove box, and immersed in a diethylene glycol dimethyl ether solution containing 1 mol / kg of LiN (SO ₂ CF ₃ ) ₂ at room temperature for 24 hours in the ionic polymer. Contained the solution. Thereafter, the ionic polymer was taken out, and the solution remaining on the surface of the ionic polymer was wiped off with a filter paper and removed to obtain a polymer electrolyte. The film thickness of the obtained polymer electrolyte was 160 μm, the content of the ionic polymer in the polymer electrolyte was 51% by weight, and the ionic conductivity was 1.4 × 10 ⁻⁴ S / cm. It was.

（スルホン酸リチウム基（ＳＯ_３Ｌｉ）を有するイオン性高分子膜の合成）
実施例１で得た上記式（１６）で表される高分子膜を１Ｎ水酸化リチウム水溶液に浸漬して対イオンがリチウムイオンであるイオン性高分子を得た。得られたイオン性高分子のイオン交換容量を測定したところ、イオン交換容量は、１．６０ミリ当量／ｇであった。得られたイオン性高分子を１２０℃で１５時間真空乾燥し、膜厚を測定したところ、膜厚は１３５μｍであった。 [Comparative Example 1] Synthesis and ionic conductivity of ionic polymer (following formula (18))

(Synthesis of ionic polymer membrane having lithium sulfonate group (SO ₃ Li))
The polymer film represented by the above formula (16) obtained in Example 1 was immersed in a 1N lithium hydroxide aqueous solution to obtain an ionic polymer whose counter ion was lithium ion. When the ion exchange capacity of the obtained ionic polymer was measured, the ion exchange capacity was 1.60 meq / g. The obtained ionic polymer was vacuum-dried at 120 ° C. for 15 hours, and the film thickness was measured. The film thickness was 135 μm.

(Ionic conductivity of ionic polymer (the above formula (18)))
The vacuum-dried ionic polymer is cut into 4 cm squares in an argon glove box, and immersed in a diethylene glycol dimethyl ether solution containing 1 mol / kg of LiN (SO ₂ CF ₃ ) ₂ at room temperature for 24 hours to obtain a solution in the ionic polymer. Was included. Thereafter, the ionic polymer was taken out, and the solution remaining on the surface of the ionic polymer was wiped off with a filter paper and removed to obtain a polymer electrolyte. The film thickness of the obtained polymer electrolyte is 137 μm, the content of the ionic polymer in the polymer electrolyte is 91% by weight, and it can be seen that the ionic polymer can hardly hold the solution. The ionic conductivity was as low as 1.5 × 10 ⁻⁶ S / cm.

[Comparative Example 2] Synthesis and ion conductivity of polystyrene sulfonimide lithium (synthesis of polystyrene sulfonyl chloride)
N, N-dimethylformamide (80 mL) was added to 10 g of sodium polystyrene sulfonate (manufactured by Aldrich, molecular weight 1 million, product number 434574), and cooled to 0 ° C. After thionyl chloride (29.5 g) was added dropwise to this solution, the mixture was stirred at room temperature for 4 hours to convert sodium sulfonate groups into SO ₂ Cl groups. After completion of the reaction, the obtained polymer was washed with water until the washing solution became neutral, then further washed with ethanol, and vacuum-dried at 60 ° C. for 20 hours. White solid was obtained was measured for ^IR, 1171cm ^-1, confirming the peak of _SO 2 Cl group to 1374cm ^-1.

(Synthesis of polystyrene sulfonimide lithium)
5 g of the obtained polymer was put in 60 g of a diethylene glycol dimethyl ether solution in which 18 g of CF ₃ SO ₂ NH ₂ and 24 g of (i-Pr) ₂ EtN were dissolved, and stirred at 130 ° C. for 20 hours. After removing the diethylene glycol dimethyl ether solution, the resulting polymer was stirred in a 10% by weight sulfuric acid aqueous solution to obtain a uniform solution. The obtained solution was gradually poured into hexane to obtain a white precipitate. Subsequently, it stirred for 2 hours in 1N lithium hydroxide aqueous solution, and the polystyrene sulfonimide lithium was obtained by pouring the obtained solution gradually in hexane. The obtained polymer was vacuum dried at 120 ° C. for 20 hours and then subjected to IR measurement. As a result, disappearance of the SO ₂ Cl group peak and a peak of the sulfonimide group at 1327 cm ⁻¹ were confirmed. It was also confirmed by the side reaction that a small amount of sulfonic acid group was present.
When the vacuum-dried ionic polymer was immersed in a propylene carbonate solution containing 1 mol / kg of LiN (SO ₂ CF ₃ ) ₂ , the solid shape could not be maintained and dissolved. This is because it does not have a repeating unit having an aliphatic hydrocarbon that does not dissolve in the non-aqueous solvent.

Claims (8)

An ionic polymer containing a repeating unit composed of an aliphatic hydrocarbon and a repeating unit having a sulfonimide group, wherein the repeating unit having a sulfonimide group has the following formula (3):

{Wherein R ¹ is a group selected from the group consisting of a fluorine atom, an alkyl group having 1 to 8 carbon atoms, and a fluoroalkyl group, M is a proton or a lithium ion, and R ^{4 to} R ⁷ are R ⁸ is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a C 1-4 fluoroalkyl group, and a C 1-4 alkyl group, and R ⁸ is a C 1-4 fluoroalkyl group, A group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms having an ether group, and an alkyl group having 1 to 4 carbon atoms having an ether group, and m, and n is an integer of 0-4. } The said ionic polymer characterized by the above-mentioned. The repeating unit comprising the aliphatic hydrocarbon has the following formula (2):

{Wherein R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms. } The ionic polymer of Claim 1 represented by these. The repeating unit having a sulfonimide group has the following formula (4):

{Wherein R ¹ , M, R ⁸ , and n are the same as those defined in Formula (3). } The ionic polymer of Claim 1 or 2 represented by these. The content of the repeating unit having a sulfonimide group represented by the formula (3) is 1 mol% or more and 100 mol% or less of the repeating unit composed of the aliphatic hydrocarbon represented by the formula (2). The ionic polymer according to claim 2 .   The ionic polymer according to any one of claims 1 to 4, wherein the ion exchange capacity of the ionic polymer is 0.5 meq / g or more and 3.0 meq / g or less.   A polymer electrolyte comprising the ionic polymer according to any one of claims 1 to 5 and a nonaqueous solvent or water. The following steps:
(I) The following formula (5):

{Wherein R ² and R ³ are hydrogen or an alkyl group having 1 to 4 carbon atoms. } And a repeating unit consisting of an aliphatic hydrocarbon represented by the following formula (6):

^{Wherein, R 4 to R ⁷ is a hydrogen atom, a fluorine atom, a fluoroalkyl group having 1 to 4 carbon atoms, and a group selected from the group consisting of alkyl group having 1 to 4 carbon atoms, ^{R 8} is From the group consisting of a fluoroalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms having an ether group, and an alkyl group having 1 to 4 carbon atoms having an ether group The selected groups, m and n are integers from 0 to 4 and X is a halogen atom. }, A repeating unit having a sulfonyl halide group represented by:
In the presence of a basic compound, a copolymer consisting of the following formula (7):
R ¹ SO ₂ NH ₂ (7)
{Wherein R ¹ is a group selected from the group consisting of a fluorine atom, an alkyl group having 1 to 8 carbon atoms, and a fluoroalkyl group. And a sulfonamide compound represented by the following formula: (II) acid-washing the obtained sulfonimide,
The method for producing an ionic polymer according to any one of claims 1 to 5, wherein in formula (3), M is a proton.   The method according to claim 1, further comprising a step of contacting the ionic polymer produced by the method according to claim 7 with a lithium compound, wherein M is lithium ion in formula (3). The manufacturing method of ionic polymer as described.