JP2006152009A - Sulfonated aromatic polyimide and electrolyte film composed of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sulfonated aromatic polyimide having high endurance under high-temperature acidic environment, excellent in mechanical strength, having high proton conductivity under low humidity and a large barrier property to a gas and a liquid when formed as a film. <P>SOLUTION: The sulfonated polyimide has a structure in which sulfonic acid groups do not exist on the main chain and aromatic rings to which the side chains where sulfonic acid groups exist among the aromatic ring constituting the main chain join to aromatic rings forming imide rings through ether bonds, sulfide bonds or sulfonyl bonds. A cation exchanger and an electrolyte film for fuel cells are each composed of the polyimide. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel sulfonated aromatic polyimide. The present invention also relates to a cation exchanger made of the polyimide, particularly to an electrolyte membrane.

  The aromatic diamino compound is used as a raw material for resin production such as polyamide and polyimide. Aromatic polyimide is generally obtained by polycondensation of an aromatic diamine such as oxydianiline and a tetracarboxylic dianhydride such as pyromellitic anhydride, and between the diamine residue and the acid anhydride residue. Because of the strong intermolecular interaction based on the charge transfer interaction, it has excellent thin film forming ability, mechanical strength, heat resistance, solvent resistance, and chemical stability, so super engineering plastics, interlayer insulation materials, etc. It is used in electronic materials or hollow fiber gas separation membranes. These excellent properties are also necessary for ion exchange membranes and electrolyte membranes for fuel cells, and polyimides having ion exchange groups such as sulfonic acid groups (also called sulfo groups) and phosphoric acid groups are good. It is expected as an electrolyte membrane for fuel cells. However, polyimide has a drawback that the imide ring is easily hydrolyzed in an acidic aqueous solution, which is a major weakness compared to other sulfonated aromatic hydrocarbon polymers such as sulfonated polyphenylene and sulfonated polyethersulfone, The solution is a critical issue.

  Therefore, a polyimide having a 6-membered ring imide ring from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) is more resistant to hydrolysis than a 5-membered imide ring from phthalic anhydride. (Non-Patent Document 1), for example, in Patent Document 1, NTDA, sulfonated diamines represented by the following chemical formulas (19) to (21) and non-sulfonated diamines (for example, oxydianiline) and It is disclosed that the copolymerized polyimide membrane is excellent as an electrolyte membrane for a fuel cell. However, the water resistance of these sulfonated polyimide membranes is not sufficient, and in Patent Document 2, the sulfonated copolymerized polyimide membrane from the sulfonated diamine represented by the chemical formula (22) has further excellent water resistance. Is disclosed. This is because the electron-withdrawing sulfo group is bonded to the phenyl ring away from the phenyl ring to which the amino group is bonded, so that the basicity of the amine is high and the hydrolysis resistance of the imide ring is increased ( For example, it is considered Non-Patent Document 2).

（Ｄ_２はＯ、Ｓ、ＣＨ_２、またはＣ（ＣＦ_３）_２等、Ｒ_４〜Ｒ_７は水素原子またはアルキル基、そして、Ａｒはスルホ基を有する芳香環残基）
上記のスルホン化ポリイミドは、いずれもスルホ基が高分子主鎖に直接結合している場合である。パーフルオロスルホン酸系高分子電解質膜では、側鎖のフルオロエーテル末端にスルホ基が結合し、親水性のスルホ基部が疎水性の主鎖部からミクロ相分離し、親水性のイオンチャンネルを形成していると考えられている。同様の効果を期待してこれまでに、芳香族炭化水素系高分子の側鎖にスルホ基を導入した側鎖型のスルホン化芳香族炭化水素系高分子膜が報告されている。例えば、化学式（２３）で示される４‐（４‐スルホフェノキシ）ベンゾイル基を有するポリ‐１，４‐フェニレン（非特許文献３）、化学式（２４）で示される２‐スルホベンゾイル基を有するポリスルホン（非特許文献４）、化学式（２５）で示されるω‐スルホアルキルスルホニル基を有するポリスルホン（非特許文献５）、化学式（２６）で示されるω‐スルホアルキル基を有するポリスルホンなどの芳香族炭化水素系ポリマー（特許文献３）が挙げられる。

_{(D 2} is O, S, CH ₂ or C, _{(CF 3) 2, etc.,} R 4 to R ₇ is a hydrogen atom or an alkyl group and,, Ar is an aromatic ring residue having a sulfo group)
All of the sulfonated polyimides described above are cases in which the sulfo group is directly bonded to the polymer main chain. In a perfluorosulfonic acid polymer electrolyte membrane, a sulfo group is bonded to the fluoroether end of the side chain, and the hydrophilic sulfo group part is microphase-separated from the hydrophobic main chain part to form a hydrophilic ion channel. It is thought that With the expectation of the same effect, a side chain type sulfonated aromatic hydrocarbon polymer film in which a sulfo group is introduced into a side chain of an aromatic hydrocarbon polymer has been reported so far. For example, poly-1,4-phenylene having a 4- (4-sulfophenoxy) benzoyl group represented by the chemical formula (23) (Non-patent Document 3), polysulfone having a 2-sulfobenzoyl group represented by the chemical formula (24) (Non-patent document 4), polysulfone having an ω-sulfoalkylsulfonyl group represented by chemical formula (25) (non-patent document 5), and polysulfone having an ω-sulfoalkyl group represented by chemical formula (26). Examples thereof include hydrogen-based polymers (Patent Document 3).

ポリイミドにおいても化学式（２７）で示されるω‐スルホアルコキシ基を有するジアミン（非特許文献６、特許文献４）及び化学式（２８）で示されるスルホフェノキシ基を有するジアミン（非特許文献７）の合成とそのポリイミドの合成と物性が報告されている。これらの側鎖型スルホン化ポリイミド膜はミクロ相分離構造を有し、比較的優れた高温耐水性を有することが明らかにされている。

Synthesis of a diamine having a ω-sulfoalkoxy group represented by the chemical formula (27) (Non-patent Documents 6 and 4) and a diamine having a sulfophenoxy group represented by the chemical formula (28) (Non-patent Document 7). And the synthesis and physical properties of its polyimide have been reported. These side-chain sulfonated polyimide membranes have a microphase separation structure and have been shown to have relatively good high temperature water resistance.

その他に、側鎖にスルホ基を有するものとして、主鎖の芳香族環にアルキレンエーテル結合を介してスルホン化芳香族基を結合したポリイミド（特許文献５）や下記一般式（２９）

In addition, a polyimide having a sulfo group in the side chain and a sulfonated aromatic group bonded to the aromatic ring of the main chain via an alkylene ether bond (Patent Document 5) or the following general formula (29)

（Ｒは、アルキレン、ハロゲン化アルキレン、アリーレン及びハロゲン化アリーレン、又はエーテル結合を含むもの）
に示される側鎖にスルホン酸基を有するポリイミドが示されている（特許文献６）。これらのイオン交換体のあるものは、比較的高温下での耐久性や耐加水分解性を有しているが、更なる耐加水分解性が望まれる。また、特許文献７においては、下記一般式（３０）で示される側鎖スルホ基を有する広範な種類（ポリエーテル、ポリケトン、ポリエーテルケトン、ポリスルホン等）の高分子電解質膜が示されている。

(R includes alkylene, alkylene halide, arylene and halogenated arylene, or ether bond)
Shows a polyimide having a sulfonic acid group in the side chain shown in (Patent Document 6). Some of these ion exchangers have durability at relatively high temperatures and hydrolysis resistance, but further hydrolysis resistance is desired. Patent Document 7 discloses a wide variety of polymer electrolyte membranes (polyether, polyketone, polyetherketone, polysulfone, etc.) having a side chain sulfo group represented by the following general formula (30).

（Ｘは単結合、電子吸引基または電子供与基、Ｒは単結合、‐（ＣＨ_２）_ｑ‐または‐（ＣＦ_２）_ｑ‐）
この中には、ポリイミドも含まれてはいるが、耐熱水性、ラジカル耐性に優れる好ましい繰り返し単位高分子としては、ポリイミドは除外されており、具体的な記載は全くなされていない。イミド環の加水分解性に問題があるからと考えられる。ポリフェニレン、ポリエーテル、ポリケトン、ポリエーテルケトン、ポリスルホンなどの（特許文献７において好ましいものとして記載されている）高分子は、ポリイミドに比べて繰り返し単位の耐加水分解性には優れるが、分子間相互作用がポリイミドほど強くなく、薄膜形成能や耐溶剤性に劣る。このようなスルホン化高分子では、水は優れた溶剤であり、プロトン伝導性を高めるためスルホ基を多く導入しイオン交換容量を高くすると、膜が水に溶解もしくは著しく膨潤しやすく、またこれを抑えるため架橋構造を導入すると膜が乾燥時にもろくなるなどの欠点があり、その改善が必要とされている。

(X is a single bond, electron-withdrawing group or electron-donating group, R is a single bond,-(CH ₂ ) _q-or- (CF ₂ ) _q- )
Although polyimide is included in this, polyimide is excluded as a preferable repeating unit polymer excellent in hot water resistance and radical resistance, and no specific description is made at all. It is thought that there is a problem with the hydrolyzability of the imide ring. Polymers such as polyphenylene, polyether, polyketone, polyetherketone, polysulfone and the like (described as preferred in Patent Document 7) are superior in resistance to hydrolysis of repeating units compared to polyimide. The action is not as strong as that of polyimide, and the film forming ability and solvent resistance are poor. In such a sulfonated polymer, water is an excellent solvent. If a large number of sulfo groups are introduced to increase proton conductivity and the ion exchange capacity is increased, the membrane is easily dissolved in water or significantly swelled. In order to suppress this, there is a drawback that the introduction of a crosslinked structure causes the membrane to become brittle when dried, and there is a need for improvement.

  Utilizing the excellent properties based on the strong intermolecular interaction of polyimide, it is a tough and flexible sulfonated polyimide thin film that significantly improves the hydrolysis resistance of the imide ring and has an excellent high temperature water resistance Development is needed. When sulfonated polyimide membranes developed so far are used for a long period of time, hydrolysis of the imide ring occurs and the molecular weight decreases, so the membrane may lose mechanical properties. In addition, during use at a high temperature, there may be a phenomenon that the sulfo group is eliminated over time, the ion exchange capacity is lowered, and the performance is lowered. These phenomena are particularly noticeable at high temperatures. Some of these sulfonated polyimide membranes can be effectively used as polymer electrolyte membranes under operating conditions up to about 80 ° C., but they deteriorate with time at higher temperatures, ie, temperatures exceeding 100 ° C. It was found that

  Therefore, even when used at a temperature of 100 ° C. or higher, it has long-term durability and mechanical strength, can be used in a wide temperature range, and has a low proton conductivity decrease under low humidity. Development of a polymer electrolyte membrane that can withstand use as an electrolyte membrane is desired.

  The present inventor has conducted extensive research to solve the problem of the problem. As a result, when a specific diamine compound is used as a monomer, the present inventor has extremely high heat resistance, that is, high mechanical properties even at a temperature of 100 to 120 ° C. The inventors have found that a cation exchange membrane that maintains strength and has little deterioration over time, in particular, a sulfonated polyimide membrane suitable for an electrolyte membrane for fuel cells can be obtained, and the present invention has been completed.

That is, the present invention relates to a novel polyimide having a sulfonic acid group in the side chain.
Special table 2000-551111 Japanese Patent Laid-Open No. 2003-64181 JP 2002-110174 A Japanese Patent Laid-Open No. 2004-155998 JP 2004-35891 A JP 2004-107484 A Japanese Patent Laid-Open No. 2004-256797 Polymer vol. 42, pages 5097-5105 (2001) Journal Membrane Science Vol. 230, pp. 111-120 (2004) Solid State Ionics, Vol. 147, 189-194 (2002) Macromolecular Rapid Communications, Vol. 23, 896-900 (2002) Journal Membrane Science Vol. 230, pp. 61-70 (2004) Journal Materials Chemistry Vol. 14, pp. 1062-1070 (2004) Transaction Materials Research Society Japan Vol. 29, pages 2541-2546 (2004)

  In view of the above technical background, the object of the present invention is to provide a polyimide-based cation exchanger having high mechanical strength and heat resistance and durability, particularly various electrochemical reactions, in particular, electrolytes for fuel cells and the like. When it uses for a film | membrane, it exists in providing the polyimide-type ion exchanger which can anticipate the outstanding effect.

  That is, the inventors of the present invention have a polyimide-based cation exchanger having a sulfonic acid group in the side chain for the purpose, and a special diamino compound having a sulfonic acid group in the side chain which is one component of the cation exchanger. Already provided. The present invention further provides a polyimide comprising the special diamino compound and a polyimide having higher mechanical strength and durability at high temperatures by copolycondensation of the diamino compound and a diamino compound having no sulfonic acid group. To do.

  The greatest feature of the present invention is a sulfonated polyimide obtained by using a di (aminoaryloxy), di (aminoarylthio) or di (aminoarylsulfonyl) aromatic carbonyl compound as one component.

  The present invention has the following configurations.

  [1] In the present invention, a sulfonated aromatic polyimide having a structural unit represented by the following formula (1) in the molecule and an electrolyte membrane comprising the polyimide (hereinafter also simply referred to as a sulfonated aromatic polyimide) It is.

但し、Ａｒは４価の芳香族基、Ａｒ_１は次の（ａ）〜（ｄ）に示される２価の基のうちいずれかの基。

However, Ar a tetravalent aromatic group, or a group of divalent radicals Ar ₁ is shown in the following (a) ~ (d).

（但し、Ｑは、‐Ｏ‐、‐Ｓ‐、‐ＣＯ‐、‐ＳＯ_２‐、‐ＣＨ_２‐、‐ＣＦ_２‐、‐Ｃ（ＣＨ_３）_２‐、‐Ｃ（ＣＦ_３）_２‐から選ばれる基）、Ｄ_１は‐Ｏ‐、‐Ｓ‐又は‐ＳＯ_２‐から選ばれる基、Ｒ_１は水素原子又は電子吸引性基、Ｘはスルホン酸基を有し、且つ更に置換基を有することある芳香族炭化水素基をそれぞれ表す。

(However, Q is —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —CF ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — D ₁ is a group selected from —O—, —S— or —SO ₂ —, R ₁ is a hydrogen atom or an electron-withdrawing group, X has a sulfonic acid group, and further has a substituent. Each represents an aromatic hydrocarbon group which may have

  [2] The present invention is also a sulfonated aromatic polyimide characterized in that X in the above item [1] is either (e) or (f) represented by the following formula (2).

（但し、Ｙは水素原子、ハロゲン原子、スルホン酸基又は下記式（３）〜（１６）に示す基のいずれか１つの基、ｐは０又は１の数〔但し、Ｙが水素原子又はハロゲン原子の時は１〕である。）

(Where Y is a hydrogen atom, halogen atom, sulfonic acid group or any one of groups shown in the following formulas (3) to (16), p is a number of 0 or 1 [where Y is a hydrogen atom or halogen, 1] for atoms.

（但し、（３）〜（１６）におけるｎは１〜２の整数を表す、またＴは‐Ｏ‐又は‐Ｓ‐を表す）。

(However, n in (3) to (16) represents an integer of 1 to 2, and T represents -O- or -S-).

  [3] Further, the present invention is a sulfonated aromatic polyimide characterized in that X shown in the item [1] of the present invention is a group represented by the following formula (17).

（但し、Ｚは直接芳香族環が結合したもの、‐Ｏ‐、‐Ｓ‐、‐ＳＯ_２‐、‐ＣＯ‐、‐ＣＨ_２‐、‐ＣＦ_２‐、又は‐Ｃ（ＣＦ_３）_２‐を表す。またｍは１〜１０、ｎは１〜２の整数を表す）。

(Where Z is a direct aromatic ring, -O-, -S-, -SO _2- , -CO-, -CH _2- , -CF _2- , or -C (CF ₃ ) _2- M represents 1 to 10, and n represents an integer of 1 to 2).

  [4] The present invention is a sulfonated aromatic polyimide characterized in that X shown in the item [3] of the present invention comprises a polyphenylene oxide chain or a polyphenylene sulfide chain substituted with a sulfonic acid group.

  [5] The present invention is the sulfonated aromatic polyimide described in the above items [1] to [4], wherein the sulfonated aromatic polyimide has structural units represented by the following formulas (1) and (18). .

（但し、Ａｒ、Ａｒ_１、Ｄ_１、Ｒ_１及びＸは、それぞれ発明〔１〕項乃至〔４〕項に同じ、また、Ａｒ_２は、スルホン酸基を有しない２価の芳香族基）
〔６〕本発明は、また前記発明〔５〕項における式（１）の構造単位対式（１８）の構造単位の割合が１０〜９０対９０〜１０であることを特徴とするスルホン化芳香族ポリイミドである。

(However, Ar, Ar ₁ , D ₁ , R ₁ and X are the same as those in the invention [1] to [4], respectively, and Ar ₂ is a divalent aromatic group having no sulfonic acid group)
[6] The sulfonated fragrance is characterized in that the ratio of the structural unit of the formula (1) to the structural unit of the formula (18) in the item [5] is 10 to 90 to 90 to 10. It is a group polyimide.

[7] Further, in the present invention, 2 to 30% of Ar ₂ described in the above item [5] or [6] is substituted with a trivalent aromatic group having no sulfonic acid group. It is a sulfonated aromatic polyimide characterized by forming a crosslinked structure.

  [8] The present invention is a cation exchanger comprising a sulfonated aromatic polyimide obtained by the inventions of the above [1] to [7].

  [9] The present invention is also an electrolyte membrane for a fuel cell comprising the cation exchange membrane according to the above item [8].

  The polyimide having one component of the di (aminoaryloxy), di (aminoarylthio) or di (aminoarylsulfonyl) aromatic carbonyl compound of the present invention has excellent mechanical strength and constitutes the main chain. A polyimide having a sulfonic acid group directly bonded to the ring, a polyimide having a sulfonic acid group bonded to an alkyl group or an aromatic ring via an ether bond or an alkylene bond, or a side chain aromatic ring having a sulfonic acid group is carbonyl or sulfonyl Compared to polyimides directly bonded to aminophenyl groups through electron-withdrawing groups such as groups, the polymer chains are cleaved by hydrolysis and sulfone when used under harsh conditions such as in acidic aqueous solutions at high temperatures. There is little degradation over time, such as elimination of acid groups, and there is little decrease in proton conductivity under low humidity, making it a fuel cell electrolyte membrane. When used, it can be an excellent electrolyte membrane combines high barrier properties to liquids of the hydrogen gas or the like and the methanol and the like of the fuel. That is, in the case of the polyimide of the present invention, there is no sulfonic acid group which is a hydrophilic group in the portion constituting the main chain, and the side chain aromatic ring having the sulfonic acid group is part of the main chain via the carbonyl group. The phenyl ring is further bonded to the amino aromatic ring via an aryloxy group, arylthio group or arylsulfonyl group, so that the hydrophobic polyimide polymer chain is relatively The flexible and hydrophilic sulfonic acid group-containing side chain aromatic ring has a structure far away from the imide ring, so that the hydrophobic main chain part and the hydrophilic side chain base part have a microphase separation structure. easy. Therefore, the water sorption amount is small in the hydrophobic domain of the polyimide main chain part, and the main chain becomes difficult to undergo hydrolysis when used as an electrolyte membrane. Furthermore, the sulfonic acid group is not easily hydrolyzed when the sulfonic acid group is bonded to an aromatic ring having a carbonyl group that is an electron-withdrawing group.

  The present invention essentially has a structural unit represented by the following formula (1) in the molecule.

式（１）中、Ａｒは後述する４価の芳香族基であり、Ａｒ_１は次の（ａ）〜（ｄ）に示される２価の基のうちいずれかの基である。

In formula (1), Ar is a tetravalent aromatic group described later, and Ar ₁ is any one of the divalent groups represented by the following (a) to (d).

（但し、Ｑは、‐Ｏ‐、‐Ｓ‐、‐ＣＯ‐、‐ＳＯ_２‐、‐ＣＨ_２‐、‐ＣＦ_２‐、‐Ｃ（ＣＨ_３）_２‐、‐Ｃ（ＣＦ_３）_２‐から選ばれる基）、
更に、Ｄ_１は‐Ｏ‐、‐Ｓ‐又は‐ＳＯ_２‐から選ばれる基、Ｒ_１は水素原子又はニトロ基、ニトリル基、エステル基などの電子吸引性基である。 また、Ｘはスルホン酸基を有し、且つ置換基を有することある芳香族炭化水素基である。ここで、「スルホン酸基を有し」とは、芳香族基に直接結合する場合のみでなく、置換基を介してスルホン酸基が結合している場合をも意味するものである。

(However, Q is —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —CF ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — A group selected from
Further, D ₁ is a group selected from —O—, —S— or —SO ₂ —, and R ₁ is a hydrogen atom or an electron-withdrawing group such as a nitro group, a nitrile group or an ester group. X is an aromatic hydrocarbon group which has a sulfonic acid group and may have a substituent. Here, “having a sulfonic acid group” means not only a case where it is directly bonded to an aromatic group, but also a case where a sulfonic acid group is bonded via a substituent.

  In addition, it is important that X is bonded via a carbonyl group which is an electron-withdrawing group because it makes it difficult to remove the sulfonic acid group from the polyimide.

  This substituent X must have an aromatic ring to which a sulfonic acid group that is a cation exchange group is bonded, as shown below.

  As the substituent X, (e) or (f) represented by the following formula (2) is preferably used.

（但し、Ｙは水素原子、ハロゲン原子、スルホン酸基又は下記式（３）〜（１６）に示す基のいずれか１つの基、ｐは０又は１の数〔但し、Ｙが水素原子又はハロゲン原子の時は１〕である。）

(Where Y is a hydrogen atom, halogen atom, sulfonic acid group or any one of groups shown in the following formulas (3) to (16), p is a number of 0 or 1 [where Y is a hydrogen atom or halogen, 1] for atoms.

（これら（３）乃至（１６）において、ｎは１又は２の整数である、またＴは‐Ｏ‐又は‐Ｓ‐を表す）。

(In these (3) to (16), n is an integer of 1 or 2, and T represents —O— or —S—).

  Further, X is preferably a group represented by the following formula (17) from the viewpoint of increasing the ion exchange capacity of the resulting polyimide.

（但し、ｍは２〜１０の整数、ｎは１〜２の整数、ｚは直接結合、‐Ｏ‐、‐Ｓ‐、‐ＳＯ_２‐、‐ＣＯ‐、‐ＣＨ_２‐、‐ＣＦ_２‐又は‐Ｃ（ＣＦ_３）_２‐を表す。）
また、式（１７）で示されるｚが酸素であるポリフェニレンオキサイド等、重合鎖が存在する場合、該重合鎖があまり長くなると、ポリイミド化する場合に支障を生じ、十分な重合度が得られないので、前記式（１７）におけるｍは１０程度まで、好ましくは２〜８である。

(Where m is an integer of 2 to 10, n is an integer of 1 to 2, z is a direct bond, —O—, —S—, —SO ₂ —, —CO—, —CH ₂ —, —CF ₂ — Or -C (CF ₃ ) _2- .)
In addition, when a polymer chain such as polyphenylene oxide in which z is oxygen represented by formula (17) is present, if the polymer chain is too long, it may cause trouble when polyimide is formed and a sufficient degree of polymerization cannot be obtained. Therefore, m in the formula (17) is up to about 10, preferably 2 to 8.

  The structural unit of the formula (1) described above is composed of a di (aminoaryloxy), di (aminoarylthio) or di (aminoarylsulfonyl) aromatic carbonyl compound represented by the following formula (19) and an aromatic tetracarboxylic acid dicarboxylic acid. It is formed by condensation with an aromatic carboxylic acid derivative such as an anhydride.

（但し、Ａｒ_１、Ｒ_１、Ｄ_１及びＸは式（１）に同じ）
本発明における上記モノマーの製造方法は、特に限定されるものではないが、次のスキームの例などの方法で製造することができる。

(However, Ar ₁ , R ₁ , D ₁ and X are the same as in formula (1))
Although the manufacturing method of the said monomer in this invention is not specifically limited, It can manufacture by methods, such as the example of the following scheme.

すなわち、上記スキームの例におけるビフェニルにかえて、ベンゼンやナフタレン或いはその誘導体、ビフェニルエーテル、ポリフェニレンオキサイド、ビフェニルスルホン、ジフェニルメチレンなどを用いれば、それぞれ対応するジ（アミノアリールオキシ）芳香族カルボニル化合物が得られるのである。また、アミノフェノール類にかえてアミノチオフェノール類を用いれば、対応するジ（アミノアリールチオ）芳香族カルボニル化合物が得られる。また、このスルフィド基を適当な条件下で適当な酸化剤を用いて、スルホニル基に酸化すれば対応するジ（アミノアリールスルホニル）芳香族カルボニル化合物が得られる。

That is, instead of biphenyl in the above scheme examples, benzene, naphthalene or derivatives thereof, biphenyl ether, polyphenylene oxide, biphenyl sulfone, diphenylmethylene, etc. are used to obtain the corresponding di (aminoaryloxy) aromatic carbonyl compounds. It is done. If aminothiophenols are used instead of aminophenols, the corresponding di (aminoarylthio) aromatic carbonyl compounds can be obtained. Further, when this sulfide group is oxidized to a sulfonyl group under an appropriate condition using an appropriate oxidizing agent, a corresponding di (aminoarylsulfonyl) aromatic carbonyl compound is obtained.

  In the present invention, by using these di (aminoaryloxy), di (aminoarylthio) or di (aminoarylsulfonyl) aromatic carbonyl compounds as monomers, an aryloxybenzoyl group, an aryl from the imide ring of the main chain. A polyimide having a sulfonic acid group only on a side-chain aromatic ring far away via a ruthiobenzoyl group or an arylsulfonylbenzoyl group. Therefore, in the sulfonated polyimide of the present invention, a sulfonic acid group is bonded to an alkyl group or an aromatic ring via a polyimide, an ether bond or an alkylene bond in which a sulfonic acid group is directly bonded to an aromatic ring constituting the main chain. Compared to bonded polyimides or polyimides whose side chain aromatic rings having sulfonic acid groups are directly bonded to aminophenyl groups via electron-withdrawing groups such as carbonyl or sulfonyl groups, etc. When used under mild conditions, degradation over time such as cleavage of polymer chains and elimination of sulfonic acid groups due to hydrolysis is small. The reason for this is that the sulfonic acid group, which is a hydrophilic group, does not exist in the portion constituting the main chain, and the phenyl ring in which the side chain aromatic ring having the sulfonic acid group is bonded via a carbonyl group is the reason. Furthermore, it is bonded to the amino aromatic ring via an aryloxy group, arylthio group or arylsulfonyl group, the hydrophobic polyimide polymer chain is relatively flexible, and the hydrophilic sulfonic acid group-containing side chain aromatic ring is Since the structure is far away from the imide ring, the hydrophobic main chain and the hydrophilic side chain base easily form a microphase separation structure, so the amount of water sorbed onto the hydrophobic domain of the polyimide main chain Is less susceptible to hydrolysis of the main chain when used as an electrolyte membrane, and a sulfonic acid group is bonded to an aromatic ring having a carbonyl group of an electron-withdrawing group, and a plurality of aromatic rings are bonded to one aromatic ring. Sulfonic acid group has a bond, it is determined that the hydrolysis of sulfonic acid groups is difficult to occur.

  In the present invention, the diamino unit constituting the polyimide is constituted only by the monomer of the formula (19), that is, it is also a preferred embodiment that is constituted only by the structural unit of the formula (1). For the purpose of suppressing the cation exchange capacity and for the purpose of preventing the decrease of the fixed ion concentration during the use of the diaphragm, for example, for the purpose of suppressing the increase in mechanical strength and the water absorption when the diaphragm such as an electrolyte membrane is used, the following formula (18 It is also a preferred embodiment that the structural units shown in (2) are copolycondensed or blended.

但し、Ａｒは式（１）の場合と同じであり、Ａｒ_２は２価のスルホン酸基を有しない芳香族基、例えば、フェニレン基、ビフェニレン基、ビフェニルエーテル基、ビフェニルチオエーテル基、ビフェニルスルホニル基、ビフェニルカルボニル基、ビスフェノキシフェニルスルホン基などである。

However, Ar is the same as in the formula (1), and Ar ₂ is an aromatic group having no divalent sulfonic acid group, such as a phenylene group, a biphenylene group, a biphenyl ether group, a biphenyl thioether group, or a biphenylsulfonyl group. A biphenylcarbonyl group, a bisphenoxyphenylsulfone group, and the like.

Such a structural unit of the formula (18) can be easily obtained by using a diamine compound in which an amino group is bonded to the divalent part of Ar ₂ . Examples of these combinations will be described later.

  In the present invention, the ratio between the structural unit represented by the formula (1) and the structural unit represented by the formula (18) is not particularly limited, but at least 10 mol% of the structural unit represented by the formula (1) is necessary. . Furthermore, it is preferable to make it exist 30 mol% or more. Also, 90 mol% is generally sufficient.

  Therefore, in general, the ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (18) is selected from the range of 10 to 90 to 90 to 10.

Moreover, a crosslinked structure can be formed in polyimide by substituting 2 to 30 mol%, preferably 5 to 10%, of Ar _{2 with} a trivalent aromatic group.

The means for causing the presence of such a trivalent aromatic group is to replace a part of the monomer for forming Ar _2, that is, an aromatic diamine having no sulfonic acid group, with an aromatic triamine having no sulfonic acid group. can get.

  In addition, the structural unit represented by the formula (1) and the structural unit represented by the formula (18) may be present at random in the molecule or may be unevenly distributed in a block shape. Moreover, a bridge | crosslinking may be formed at random in a polyimide molecule, and can also exist only in the site | part of the polyimide chain which does not contain the sulfonic acid group shown by Chemical formula (18).

  A polyimide having a crosslinked structure has an advantage of suppressing water absorption, suppressing swelling and deformation of a membrane during use, maintaining high proton conductivity, and improving mechanical strength.

  Among these diamino or triamino compounds having at least one aromatic ring not having a sulfonic acid group, examples of the diamino compound include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulfone, 4,4 ′ -Diaminodiphenyl sulfide, benzidine, metaphenylenediamine, paraphenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis [4- (4-aminophenoxy) phenyl] sulfone, bis- (4-aminophenoxy) Phenyl) sulfide, bis- (4-aminophenoxyphenyl) biphenyl, 1,4-bis- (4-aminophenoxy) benzene, 1,3-bis- (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether 4,4′-bis (4-amino Nophenoxy) biphenyl, bis {4- {3-aminophenoxy) phenyl} sulfone, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoro Examples include, but are not limited to, propane, 2,2-bis [4- (4-amonophenoxy) phenyl) propane, 2,2′-bis (trifluoromethyl) -benzidine and the like.

  Further, as a triamine compound, in order to facilitate a crosslinking reaction, two amino groups are not bonded to the same aromatic ring adjacent to each other, particularly two or more first amino groups are bonded to the same aromatic ring. Those which are not bonded are preferable, and for example, 1,3,5-tri (4-aminophenoxy) benzene, tri (4-aminophenyl) amine, 1,3,5-triaminobenzene and the like are preferably used.

  These triamine compounds can be mixed with a diamino compound represented by the formula (19) and a diamine having no sulfonic acid group for copolycondensation, and tetracarboxylic dianhydride and a compound of the formula (19). And (co) condensation polymerization with a diamine having no sulfonic acid group, a carboxylic acid anhydride-terminated sulfonated polyimide oligomer is synthesized by adding an excess of carboxylic acid anhydride to the diamine, followed by triamine. Can be used for producing a branched cross-linked polyimide film in which sulfonated polyimide oligomers are connected in a network.

  In the present invention, 1,4,5,8-naphthalenetetracarboxylic dianhydride has been described as a tetracarboxylic acid compound to be reacted with a diamine compound in order to constitute a polyimide. Of course, in the present invention, a tetracarboxylic acid is used. If it reacts with a diamine compound as a component and forms imide, it will not specifically limit.

  That is, in the polyimide of this invention, what is used as a monomer for general polyimide manufacture can be used as a tetracarboxylic acid component without being restrict | limited at all. For example, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3 ′, 3,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3 , 3 ′, 4,4′-diphenyl ether tetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, 1,4 5,8-naphthalenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4 '-(hexafluoroisopropylidene) diphthalic acid, m- (terphenyl) 3,4,3 ", 4 “-Tetracarboxylic acid, 1,6,7,12-perylenetetracarboxylic acid or acid dianhydrides or esterified products thereof. Among these, 1,4,5,8-naphthalenetetracarboxylic acid, or its acid dianhydride or esterified product is particularly preferable because a crosslinked sulfonated polyimide having good water resistance can be easily obtained.

  As described above, the polycondensation reaction between a diamino compound monomer (some of which includes a triamino compound) and a carboxylic acid anhydride can be used without any limitation on the means conventionally used for synthesizing polyimide. Although it is possible, a general scheme is now shown for the cases of homopolycondensation, random copolycondensation, block copolycondensation and branched bridge copolycondensation.

（これらの反応式において、ＴＥＡはトリエチルアミン、ＰｈＣＯＯＨは安息香酸、ＮＴＤＡは１，４，５，８‐ナフタレンテトラカルボン酸二無水物、Ａｒは芳香環を有する２価の基をそれぞれ表す。）
以下に実施例を示す。

(In these reaction formulas, TEA represents triethylamine, PhCOOH represents benzoic acid, NTDA represents 1,4,5,8-naphthalenetetracarboxylic dianhydride, and Ar represents a divalent group having an aromatic ring.)
Examples are shown below.

The ¹ HNMR data shown in the following Examples was measured by JEOL JEOL EX-270 using deuterated dimethyl sulfoxide (DMSO-d ₆ ) as a solvent. Moreover, the evaluation method in this invention is as follows.

[Thermogravimetric analysis]
Thermogravimetric analysis is performed with a TG-MS analyzer (TG-MS system 220) manufactured by Seiko Electronics Co., Ltd. at a heating rate of 5 ° C./min in a He stream, and sulfonic acid groups or sulfo groups at 200 to 300 ° C. The initiation temperature Td for the decomposition of the propoxy group was determined.

[Water absorption rate, Water uptake]
About 80 mg of the membrane sample was dried and the dry weight Wd was measured, and then immersed in water at 30 ° C. for 2 to 4 hours. The membrane sample was taken out of the water, the water adhering to the surface quickly was wiped off with tissue paper, and the membrane weight Ws during swelling was measured. The water absorption rate (Water uptake; WU) was determined from the following equation.
WU = (Ws−Wd) / Wd × 100%
[water resistant]
A film sample having a film thickness of 30 to 40 μm was immersed in hot water under pressure at 130 ° C. for 48 hours, and then evaluated in the following three stages from the viewpoint of film shape and strength. <1>: The film shape is not maintained. <2>: When the film was taken out with tweezers and bent as it was at 120 degrees, the film was broken. <3>: The film did not break even when bent at 120 degrees. In addition, after the membrane subjected to the pressure water immersion treatment was air-dried, proton conductivity was measured in water at 50 ° C. and evaluated from the viewpoint of proton conductivity in the following three stages. (1): The proton conductivity decreased by 20% or more by the treatment. (2): Decreased by 5 to 20%. (3): No change within experimental error (± 5%) range. [Proton conductivity]
A membrane sheet (1.0 cm x 0.5 cm) and four platinum black electrode plates are attached to the proton conductivity measurement cell and set in temperature-controlled water or a temperature / humidity-controlled chamber, manufactured by Hioki Electric Co., Ltd. The electrical resistance R was measured by the complex impedance method in the frequency range of 100 Hz to 100 kHz using an LCR meter (HIOKI 3552-80), and the proton conductivity σ was calculated from the following equation.
_{s = d / (t s w} s R)
Here, d is 2 the distance between the electrodes (0.5 cm), _{t s} and _{w s} is the thickness and width of the film sheet in RH 70% at room temperature. The calculation of proton conductivity in water, with t _s and w _s value in water.
[Methanol permeability coefficient]
A membrane sheet is sandwiched between a supply side cell (capacity 350 ml) and a permeation side cell (capacity 100 ml) of the liquid permeation measurement cell via a fluoro rubber seal plate. Put 30 wt% aqueous methanol solution to the feed side of the membrane, distilled water was placed on the transmission side, using a gas chromatograph, a liquid composition of the feed side and the permeate side at any time interval is measured, the methanol permeation coefficient P _M Asked. Note with swollen film thickness in the calculation of P _M.

Abbreviations used in the following examples are as follows.
NTDA: 1,4,5,8, -naphthalene tetracarboxylic acid TEA: triethylamine BAPSB: 2,4-bis (4-aminophenoxy) -3′-sulfobenzophenone DMSO: dimethyl sulfoxide NMP: N-methylpyrrolidone BAPSSPB: 2 , 5-bis (4-aminophenoxy) 3'-sulfo-4 '-(4-sulfophenyl) benzophenone 3,3'-BSPB: 3,3'-bis (3-sulfopropoxy) benzidine BAPPS: 4,4 '-Bis (3-aminophenoxy) phenyl sulfone BAPB: 4,4'-bis (4-aminophenoxy) biphenyl TAPB: 1,3,5-tris (4-aminophenoxy) benzene BAPBDS: 4,4'-bis (4-Aminophenoxy) biphenyl 3,3′-disulfonic acid

Sulfonated polyimide NTDA-BAPSB
(1) Synthesis of 2,4-bis (4-aminophenoxy) -3′-sulfobenzophenone (BAPSB).
(A) Synthesis of 2,4-dichloro-3′-sulfobenzophenone (Na salt) To a well-dried 100 ml three-necked flask, 7.5 g of AlCl ₃ and 15 ml of benzene were added under a nitrogen stream, and this mixture was added at 0 ° C. The solution was kept at that temperature, and a solution prepared by dissolving 5.24 g (0.025 mol) of 2,4-dichlorobenzoyl chloride in 5 ml of benzene was added dropwise. Meanwhile, the temperature was kept at 0 ° C. with stirring. After the addition, the mixture was stirred at room temperature for 10 hours. The reaction solution was poured into about 100 g of ice water (with a few drops of hydrochloric acid added). Two phases appeared, the organic phase was separated from the aqueous phase, and the organic phase was evaporated to dryness to obtain 6.1 g of 2,4-dichlorobenzophenone. Yield 97%.

Into a 100 ml three-necked flask equipped with a magnetic stirrer was charged 6.0 g (0.024 mol) of 2,4-dichlorobenzophenone, cooled in an ice bath, and slowly stirred with 6.0 ml of concentrated sulfuric acid. Added. After 2,4-dichlorobenzophenone was completely dissolved, 6.0 ml of fuming sulfuric acid (60%) was added dropwise. After the fuming sulfuric acid was added, the mixture was heated to 70 ° C. and stirred for 8 hours. After cooling to room temperature, it was slowly poured into 80 g of ice water, neutralized with sodium hydroxide solution, and the solid was filtered off. The filtrate was evaporated to dryness and 80 ml of dimethyl sulfoxide (DMSO) was added to extract the organic components in the solid. After filtering off the solid, the DMSO phase was evaporated to dryness to give 7.2 g of solid product. Yield 85%.
(I) Synthesis of BAPSB In a 100 ml four-necked flask equipped with a magnetic stirrer, 3.54 g (0.010 mol) of 2,4-dichloro-3′-sulfobenzophenone (Na salt), 4-aminophenol; 27 g (0.030 mol) and 30 ml of NMP were added under a nitrogen atmosphere. After dissolution, 2.6 g of K ₂ CO ₃ and 15 ml of toluene were added, and the mixture was stirred and heated at 130 ° C. for 4 hours under a nitrogen stream. The produced water was removed out of the reaction system as an azeotrope with toluene. Further, the reaction mixture was stirred at 160 ° C. for 20 hours. The reaction mixture was cooled to room temperature and then added to 300 ml of cold water, and then concentrated hydrochloric acid was slowly added until the pH of the solution was about 1. The resulting solid precipitate was filtered off and dried to give 3.10 g of solid product. Yield 65%. This was analyzed by ¹ HNMR (270 MHz, triethylamine-containing DMSO-d ₆ ) at δ: 5.0 (—NH ₂ ), 6.25 (1H), 6.5-6.7 (8H), 6.8 (1H ), 7.4-7.8 (5H). Further, it was confirmed by BFTB (Chemical Formula 55) by FT-IR.

（２）スルホン化ポリイミドＮＴＤＡ‐ＢＡＰＳＢの合成
乾燥した１００ｍｌの四口フラスコ中で１．９０４ｇ（４．０ミリモル）のＢＡＰＳＢと２．１ｍｌのトリエチルアミン（ＴＥＡ）を１６ｍｌのｍ−クレゾールに加えて溶かし、次いで、１．０７２ｇ（４．０ミリモル）の１，４，５，８‐ナフタレンテトラカルボン酸二無水物（ＮＴＤＡ）および０．６８ｇの安息香酸を加え、窒素ガス雰囲気下で混合物を８０℃で４時間そして１８０℃で１０時間攪拌し、１０ｍｌのＮＭＰを添加してさらに１８０℃で１０時間攪拌した。重合反応液を８０℃まで冷却後、１０ｍｌのＮＭＰを加え希釈後、多量のアセトンに投入し、析出した固体を濾別し、アセトン洗浄後乾燥した。得られた生成物の溶液粘度η_ＳＰ／ｃ（溶媒：１ｗｔ％のＬｉＣｌ含有ＤＭＳＯ；０．５ｗｔ％；３５℃）は１．５ｄｌ／ｇであった。生成物をＤＭＳＯに溶解し、ガラス板上に流延し、８０℃で１０時間乾燥して、ＴＥＡ塩型のスルホン化ポリイミド膜を得た。これをメタノールに２日間浸漬し、次いで０．５Ｍ硫酸溶液に２日間浸漬しプロトン交換した後、水洗し１５０℃で１０時間真空乾燥してプロトン型のスルホン化ポリイミドＮＴＤＡ‐ＢＡＰＳＢ（化５６）膜を得た。この膜の特性評価結果を表１に示す。

(2) Synthesis of sulfonated polyimide NTDA-BAPSB In a dry 100 ml four-necked flask, 1.904 g (4.0 mmol) of BAPSB and 2.1 ml of triethylamine (TEA) were dissolved in 16 ml of m-cresol. 1.072 g (4.0 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and 0.68 g of benzoic acid are then added and the mixture is heated to 80 ° C. under a nitrogen gas atmosphere. For 4 hours and at 180 ° C. for 10 hours, 10 ml of NMP was added and the mixture was further stirred at 180 ° C. for 10 hours. The polymerization reaction solution was cooled to 80 ° C., diluted with 10 ml of NMP, poured into a large amount of acetone, the precipitated solid was filtered off, washed with acetone and dried. The solution viscosity η _SP / c (solvent: 1 wt% LiCl-containing DMSO; 0.5 wt%; 35 ° C.) of the obtained product was 1.5 dl / g. The product was dissolved in DMSO, cast on a glass plate, and dried at 80 ° C. for 10 hours to obtain a TEA salt type sulfonated polyimide membrane. This was immersed in methanol for 2 days, then immersed in a 0.5 M sulfuric acid solution for 2 days to exchange protons, washed with water, and vacuum dried at 150 ° C. for 10 hours to form a proton-type sulfonated polyimide NTDA-BAPSB (Chemical Formula 56) membrane. Got. Table 1 shows the characteristic evaluation results of this film.

Sulfonated polyimide NTDA-BAPSSPB
(1) Synthesis of 2,5-bis (4-aminophenoxy) 3′-sulfo-4 ′-(4-sulfophenyl) benzophenone (BAPSSPB) (a) 2,5-dichloro-3′-sulfo-4 ′ Synthesis of-(4-sulfophenyl) benzophenone (Na salt) A well-dried 100 ml three-necked flask was charged with 5.28 g AlCl _3, 5.55 g (0.036 mol) biphenyl and 20 ml 1,2-dichloroethane with nitrogen. The mixture was dissolved under a stream of air, the mixture was cooled to 0 ° C., kept at that temperature, and a solution of 7.54 g (0.036 mol) of 2,5-dichlorobenzoyl chloride dissolved in 20 ml of 1,2-dichloroethane was added. Added dropwise. Meanwhile, the temperature was kept at 0 ° C. with stirring. After the addition, the mixture was stirred at room temperature for 10 hours. The reaction solution is poured into about 100 g of ice water (with a few drops of hydrochloric acid added), then 200 ml of benzene are added, the organic phase is separated from the aqueous phase, the organic phase is evaporated to dryness and 2,5-dichloromethane is added. 10.60 g of -4′-phenylbenzophenone was obtained. Yield 90%.

Into a 100 ml three-necked flask equipped with a magnetic stirrer was added 8.18 g (0.025 mol) of 2,5-dichloro-4′-phenylbenzophenone, cooled in an ice bath, and then stirred with 8.0 ml of concentrated sulfuric acid. Slowly added. After 2,5-dichloro-4'-phenylbenzophenone was completely dissolved, 8.0 ml of fuming sulfuric acid (60%) was added dropwise. After the fuming sulfuric acid was added, the mixture was slowly heated to 90 ° C. and stirring was continued for 10 hours. After cooling to room temperature, it was slowly poured into 100 g of ice water, neutralized with sodium hydroxide solution, and the solid was filtered off. The filtrate was dried and 80 ml of dimethyl sulfoxide (DMSO) was added to extract the organic components in the solid. After the solid was filtered off, the DMSO phase was concentrated to dryness to obtain 11.29 g of a solid product. Yield 85%.
(I) Synthesis of BAPSSPB In a 100 ml four-necked flask equipped with a magnetic stirrer, 4.25 g (0.2 mg of 2,5-dichloro-3′-sulfo-4 ′-(4-sulfophenyl) benzophenone (Na salt) was added. 008 mol) and 30 ml of NMP were added under a nitrogen atmosphere. After dissolution, 2.62 g (0.024 mol) of 4-aminophenol, 2.07 g (0.015 mol) of K ₂ CO ₃ and 15 ml of toluene were added, and the mixture was stirred and heated at 130 ° C. for 4 hours under a nitrogen stream. The produced water was removed out of the reaction system as an azeotrope with toluene. The reaction mixture was stirred at 160 ° C. for 20 hours. The reaction mixture was cooled to room temperature and then added to 300 ml of cold water, and then concentrated hydrochloric acid was slowly added until the pH of the solution was about 1. The resulting solid precipitate was filtered off and dried to give 2.53 g of solid product. Yield 50%. This was analyzed by ¹ HNMR (270 MHz, DMSO-d ₆ containing triethylamine) at δ: 5.0 (—NH ₂ ), 6.4-6.6 (8H), 6.7-6.8 (2H), 7 It showed a peak of .6-8.4 (8H). Moreover, it was confirmed by BAFTSPB (Chemical Formula 57) by FT-IR.

（２）ＮＴＤＡ‐ＢＡＰＳＳＰＢの合成
乾燥した１００ｍｌの四口フラスコ中で２．５２８ｇ（４．０ミリモル）のＢＡＰＳＳＰＢと１．４ｍｌのＴＥＡを１６ｍｌのｍ−クレゾールに加えて溶かし、次いで、１．０７２ｇ（４．０ミリモル）のＮＴＤＡおよび０．６８ｇの安息香酸を加え、窒素ガス雰囲気下で混合物を８０℃で4時間そして１８０℃で１０時間攪拌し、１０ｍｌのＮＭＰを添加してさらに１８０℃で１０時間攪拌した。重合反応液を８０℃まで冷却後、１０ｍｌのＮＭＰを加え希釈後、多量のアセトンに投入し、析出した固体を濾別し、アセトン洗浄後乾燥した。得られた生成物の溶液粘度η_ＳＰ／ｃ（溶媒：１ｗｔ％のＬｉＣｌ含有ＤＭＳＯ；０．５ｗｔ％；３５℃）は２．５ｄｌ／ｇであった。生成物をＤＭＳＯに溶解し、ガラス板上に流延し、８０℃で１０時間乾燥して、ＴＥＡ塩型のスルホン化ポリイミド膜を得た。これをメタノールに２日間浸漬し、次いで０．５Ｍ硫酸溶液に２日間浸漬しプロトン交換した後、水洗し１５０℃で１０時間真空乾燥してプロトン型のスルホン化ポリイミドＮＴＤＡ‐ＢＡＰＳＳＢ膜を得た。この膜の特性評価結果を表１に示す。プロトン伝導度の温度依存性を図１に示す。

(2) Synthesis of NTDA-BAPSSPB In a dry 100 ml four-necked flask, 2.528 g (4.0 mmol) of BAPSSPB and 1.4 ml of TEA were dissolved in 16 ml of m-cresol, and then 1.072 g (4.0 mmol) NTDA and 0.68 g benzoic acid are added and the mixture is stirred at 80 ° C. for 4 hours and at 180 ° C. for 10 hours under a nitrogen gas atmosphere, 10 ml of NMP is added and an additional 180 ° C. is added. Stir for 10 hours. The polymerization reaction solution was cooled to 80 ° C., diluted with 10 ml of NMP, poured into a large amount of acetone, the precipitated solid was filtered off, washed with acetone and dried. The solution viscosity η _SP / c (solvent: DMSO containing LiCl of 1 wt%; 0.5 wt%; 35 ° C.) of the obtained product was 2.5 dl / g. The product was dissolved in DMSO, cast on a glass plate, and dried at 80 ° C. for 10 hours to obtain a TEA salt type sulfonated polyimide membrane. This was immersed in methanol for 2 days, then immersed in a 0.5 M sulfuric acid solution for 2 days to exchange protons, washed with water and vacuum dried at 150 ° C. for 10 hours to obtain a proton-type sulfonated polyimide NTDA-BAPSSB membrane. Table 1 shows the characteristic evaluation results of this film. The temperature dependence of proton conductivity is shown in FIG.

Random copolymerized sulfonated polyimide NTDA-BAPSSPB / BAPPS (3/1) -r
BAPSSPB synthesized in Example 2 was used as the sulfonated diamine, and 4,4′-bis (3-aminophenoxy) phenylsulfone (BAPPS) was used as the non-sulfonate diamine. In a dry 100 ml four-necked flask, 1.898 g (3.0 mmol) BAPSSPB and 1.1 ml TEA were dissolved in 20 ml m-cresol and then 0.433 g (1.0 mmol) BAPPS. After adding 1.072 g (4.0 mmol) of NTDA and 0.68 g of benzoic acid, the mixture was stirred at 80 ° C. for 4 hours and at 180 ° C. for 20 hours, 10 ml of m-cresol was added and further stirred at 180 ° C. for 10 hours. The polymerization reaction solution was cooled to 80 ° C., diluted with 10 ml of m-cresol, poured into a large amount of acetone, the precipitated solid was filtered off, washed with acetone and dried. The solution viscosity η _SP / c (solvent: 1 wt% LiCl-containing DMSO; 0.5 wt%; 35 ° C.) of the obtained product was 2.0 dl / g. The product was dissolved in DMSO, cast on a glass plate, and dried at 80 ° C. for 10 hours to obtain a TEA salt type copolymer sulfonated polyimide membrane. This was immersed in methanol for 2 days, then immersed in a 0.5 M sulfuric acid solution for 2 days to exchange protons, washed with water and vacuum dried at 150 ° C. for 10 hours to obtain proton type random copolymer sulfonated polyimide NTDA-BAPSSPB / BAPPS. A (3/1) -r film was obtained. Table 1 shows the characteristic evaluation results of this film. The temperature dependence of proton conductivity is shown in FIG.

Sequenced copolymerized sulfonated polyimide NTDA-BAPSSPB / BAPPS (2/1) -s
BAPSSPB synthesized in Example 2 was used as the sulfonated diamine, and BAPPS was used as the non-sulfonate diamine. In a dry 100 ml four-necked flask, 1.898 g (3.0 mmol) BAPSSPB and 1.2 ml TEA were dissolved in 10 ml m-cresol and then 0.965 g (3.6 mmol) NTDA and 0.62 g of benzoic acid was added and the mixture was stirred at 80 ° C. for 4 hours and at 180 ° C. for 5 hours under a nitrogen gas atmosphere. The solution was cooled to room temperature and 0.650 g (1.5 mmol) of BAPPS, 0.241 g (0.9 mmol) of NTDA, 0.153 g of benzoic acid and 10 ml of m-cresol were sequentially added at 80 ° C. The mixture was stirred for 4 hours at 180 ° C. for 20 hours. The polymerization reaction solution was cooled to 80 ° C., diluted with 10 ml of m-cresol, poured into a large amount of acetone, the precipitated solid was filtered off, washed with acetone and dried. The solution viscosity η _SP / c (solvent: DMSO containing LiCl of 1 wt%; 0.5 wt%; 35 ° C.) of the obtained product was 2.2 dl / g. The product was dissolved in DMSO, cast onto a glass plate, and dried at 80 ° C. for 10 hours to obtain a TEA salt type copolymer sulfonated polyimide membrane. This was immersed in methanol for 2 days, then immersed in a 0.5 M sulfuric acid solution for 2 days to exchange protons, washed with water and vacuum-dried at 150 ° C. for 10 hours to obtain proton type sequence copolymerized sulfonated polyimide NTDA-BAPSSPB / A BAPPS (2/1) -s film was obtained. Table 1 shows the characteristic evaluation results of this film.

Branched and crosslinked sulfonated polyimide NTDA-BAPSSPB / TAPB (5/4)
(1) Synthesis of 1,3,5-tris (4-aminophenoxy) benzene (TAPB) 49.6 g (0.35 mol) of 4-fluoronitrobenzene, 12.6 g (0.1 mol) of 1,3,5 -Trihydroxybenzene and 20.7 g (0.15 mol) of potassium carbonate were added to a mixed solution of 200 ml of DMSO and 50 ml of toluene and heated under a nitrogen stream. The produced water was removed while refluxing toluene at 140 ° C. for 4 hours. While removing toluene, the temperature was raised to 175 ° C. and heated for 16 hours. The reaction solution was cooled, poured into a large amount of methanol, and the precipitated solid product was washed with water and dried.

30 g of the obtained solid, 60 mg of iron (III) chloride and 2 g of carbon on platinum were added to 110 ml of 2-methoxyethanol, the mixture was heated to 90 ° C., and 18.9 g of hydrazine monohydrate was added dropwise over 2 hours. did. The reaction solution was heated at 110 ° C. for 2 hours, cooled to room temperature, and filtered. 20 ml of concentrated hydrochloric acid was added to the filtrate to precipitate a solid. The solid was filtered off and dried to give a yellow solid of TAPB.
(2) Synthesis of Branched Crosslinked Sulfonated Polyimide NTDA-BAPSSPB / TAPB (5/4) BAPSSPB synthesized in Example 2 was used as a sulfonated diamine. In a dry 100 ml four-necked flask, 2.528 g (4.0 mmol) BAPSSPB and 1.4 ml TEA were dissolved in 20 ml m-cresol and then 1.34 g (5.0 mmol) NTDA and 0.85 g of benzoic acid was added and the mixture was stirred at 80 ° C. for 4 hours and at 180 ° C. for 20 hours under a nitrogen gas atmosphere. The solution was cooled to room temperature, 0.340 g (0.67 mmol) of TAPB and 20 ml of NMP were added, and the mixture was stirred at 60 ° C. for 4 hours. The obtained solution was cast on a glass plate and dried by heating at 80 ° C., 95 ° C., and 110 ° C. for 1 hour, 130 ° C. for 8 hours, and 200 ° C. for 10 hours, respectively. A polyimide film was obtained. This was immersed in methanol for 2 days, then immersed in a 0.5 M sulfuric acid solution for 2 days to exchange protons, washed with water and vacuum dried at 150 ° C. for 10 hours to form proton-type branched cross-linked sulfonated polyimide NTDA-BAPSSPB / TAPB ( 5/4) A membrane was obtained. Table 1 shows the characteristic evaluation results of this film.

Comparative Example 1

Random copolymerized sulfonated polyimide NTDA-BAPBDS / BAPB (2/1) -r
4,4′-bis (4-aminophenoxy) biphenyl-3,3′-disulfonic acid (BAPBDS) was synthesized by the method described in JP-A-2003-68326. BAPBDS was used as the sulfonated diamine, and 4,4′-bis (3-aminophenoxy) phenylsulfone (BAPPS) was used as the non-sulfonate diamine. In a dry 100 ml four-necked flask, 1.056 g (2.0 mmol) BAPBDS and 0.68 ml TEA were dissolved in 12 ml m-cresol and then 0.368 g (1.0 mmol) BAPB. After adding 0.84 g (3.0 mmol) of NTDA and 0.51 g of benzoic acid, the mixture was stirred at 80 ° C. for 4 hours and at 180 ° C. for 20 hours. The polymerization reaction solution was cooled to 80 ° C., diluted with 20 ml of m-cresol, poured into a large amount of acetone, the precipitated solid was filtered off, washed with acetone and dried. The solution viscosity η _SP / c (solvent: m-cresol; 0.5 wt%; 35 ° C.) of the obtained product was 2.8 dl / g. The product was dissolved in m-cresol, cast on a glass plate, and dried at 120 ° C. for 10 hours to obtain a TEA salt type copolymer sulfonated polyimide membrane. This was immersed in methanol for 2 days, then immersed in 0.5 M sulfuric acid solution for 2 days to exchange protons, washed with water and vacuum dried at 150 ° C. for 10 hours to obtain proton type random copolymer sulfonated polyimide NTDA-BAPBDS / BAPB. A (2/1) -r film was obtained. Table 1 shows the characteristic evaluation results of this film. The temperature dependence of proton conductivity is shown in FIG.

Comparative Example 2

Random copolymerized sulfonated polyimide NTDA-3,3'-BSPB / BAPPS (2/1) -r
3,3′-bis (3-sulfopropoxy) benzidine (3,3′-BSPB) was synthesized by the method described in JP-A-2004-155998. Random in the same manner as in Comparative Example 1 except that 0.96 g (2.0 mmol) of 3,3′-BSPB was used as the sulfonated diamine and 0.433 g (1.0 mmol) of BAPPS was used as the non-sulfonate diamine. Copolymerized sulfonated polyimide NTDA-3,3′-BSPB / BAPPS (2/1) -r membrane was obtained. Table 1 shows the characteristic evaluation results of this film. The temperature dependence of proton conductivity is shown in FIG.

Comparative Example 3

Perfluorosulfonic acid-based electrolyte membrane A perfluorosulfonic acid-based electrolyte membrane (manufactured by Company D, thickness 50 μm) was used. Table 1 shows the characteristic evaluation results of this film.
Summary of Evaluation Results (1) The homosulfonated polyimide membrane of Example 2 has a relatively high IEC and a relatively high WU, but has excellent high-temperature water resistance in terms of membrane strength. The copolymerized sulfonated polyimide membrane of Example 3 has almost the same IEC as the main chain copolymerized sulfonated polyimide membrane of Comparative Example 1, but the high-temperature water resistance in terms of membrane strength is higher than that of Comparative Example 1. Are better. The sulfonated polyimide membrane in this patent has a microphase-separated structure and has excellent high-temperature water resistance from the viewpoint of membrane strength even with a relatively high IEC. This is superior to the main-chain sulfonated polyimide membrane of Comparative Example 1.

  (2) As in Examples 1 to 5, the decomposition temperature of the sulfonic acid group is 290 to 295 ° C., which is 30 to 40 ° C. higher than the side chain sulfonated polyimide membrane having the sulfoalkoxy group of Comparative Example 2, Moreover, it is excellent in high-temperature water resistance from the viewpoint of proton conductivity. This indicates that the sulfonated polyimide membrane in this patent is less susceptible to sulfonic acid group elimination in high-temperature water, and is superior in this respect to the side chain sulfonated polyimide membrane of Comparative Example 2. .

(3) Compared with Comparative Examples 1 and 2, the sulfonated polyimide membrane in this patent has high proton conductivity, and in particular, the decrease in proton conductivity at low humidity is compared with the sulfonated polyimide of Comparative Example. Smaller than that. (Table 1 and Figure 1)
(4) The sulfonated polyimide membrane in this patent has a high proton conductivity without a decrease in proton conductivity even at a high temperature of 100 ° C. or higher. (Figure 2)
(5) From the above results, the sulfonated polyimide membrane in this patent is suitable as a polymer electrolyte membrane for high-temperature PEFC.

(6) The sulfonated polyimide membrane in this patent has a very low methanol permeability coefficient compared to the perfluorosulfonic acid membrane of Comparative Example 3, and the ratio of proton conductivity to methanol permeability coefficient φ (φ = σ / P _M ) is four times or more larger and is suitable as a polymer electrolyte membrane for direct methanol fuel cells.

  The present invention is a polyimide that is a solid electrolyte with high proton conductivity, high heat resistance, and high mechanical strength. When used as a cation exchanger or as a diaphragm for various electrolysis, it has barrier properties against gases and liquids. It is large and particularly has excellent properties as an electrolyte membrane for fuel cells.

Indicates the temperature dependence of proton conductivity.

Claims (9)

A sulfonated aromatic polyimide having a structural unit represented by the following formula (1) in a molecule.

However, Ar is a tetravalent aromatic group, or a group of divalent radicals Ar ₁ is shown in the following (a) ~ (d).

(However, Q is —O—, —S—, —CO—, —SO ₂ —, —CH ₂ —, —CF ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — D ₁ is a group selected from —O—, —S— or —SO ₂ —, R ₁ is a hydrogen atom or an electron withdrawing group, X has a sulfonic acid group, and is further substituted. An aromatic hydrocarbon group that may have a group. The sulfonated aromatic polyimide according to claim 1, wherein X is either (e) or (f) represented by the following formula (2).

(Where Y is a hydrogen atom, halogen atom, sulfonic acid group or any one of groups shown in the following formulas (3) to (16), p is a number of 0 or 1 [where Y is a hydrogen atom or halogen, 1] for atoms.

(However, n in (3) to (16) represents an integer of 1 to 2, and T represents -O- or -S-.) The sulfonated aromatic polyimide according to claim 1, wherein X is a group represented by the following formula (17).

(Where Z is a direct aromatic ring, -O-, -S-, -SO _2- , -CO-, -CH _2- , -CF _2- , or -C (CF ₃ ) _2- , M represents an integer of 1 to 10, and n represents an integer of 1 to 2.)   The sulfonated aromatic polyimide according to claim 1, wherein X comprises a polyphenylene oxide chain or a polyphenylene sulfide chain substituted with a sulfonic acid group. The sulfonated aromatic polyimide according to any one of claims 1 to 4, which has a structural unit represented by the following formulas (1) and (18).

However, Ar, Ar ₁ , D ₁ , R ₁ and X are the same as in claim 1, Ar ₂ is a divalent aromatic group having no sulfonic acid group,   The sulfonated aromatic polyimide according to claim 5, wherein the ratio of the structural unit of formula (1) to the structural unit of formula (18) is 10 to 90 to 90 to 10. The sulfonated aromatic polyimide according to claim 5 or 6, wherein 2 to 30% of Ar ₂ is substituted with a trivalent aromatic group having no sulfonic acid group to form a crosslinked structure. .   A cation exchanger comprising the sulfonated aromatic polyimide according to any one of claims 1 to 7.   An electrolyte membrane for a fuel cell comprising the cation exchanger according to claim 8.

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