JP2007230857A - Modified free acid type heteropolyacid and fixed modified free acid type heteropolyacid - Google Patents
Modified free acid type heteropolyacid and fixed modified free acid type heteropolyacid Download PDFInfo
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Abstract
Description
本発明は酸触媒として使用できる修飾フリーアシッド型ヘテロポリ酸、およびこれを用いた固定化修飾フリーアシッド型ヘテロポリ酸に関する。 The present invention relates to a modified free acid type heteropolyacid that can be used as an acid catalyst, and an immobilized modified free acid type heteropolyacid using the same.
ヘテロポリ酸塩は酸素原子が４個配位したＰ、Ｓｉ、Ａｓ、Ｇｅ、Ｓなどのヘテロ原子を中心にＷ、Ｍｏ等の骨格構成原子が酸素原子を介して配位した構造を有するものである。このような構造を有するヘテロポリ酸塩は骨格構成原子の一部を欠損させ、異種金属で置換することが可能であることが知られている。このような欠損型のヘテロポリ酸塩と、より酸化数の低い異種金属で置換されたヘテロポリ酸塩は表面の負電荷密度が通常のヘテロポリ酸塩と比較して増大しているために反応用触媒として使用されている。 Heteropolyacid salts have a structure in which skeleton constituent atoms such as W and Mo are coordinated through oxygen atoms centered on heteroatoms such as P, Si, As, Ge, and S in which four oxygen atoms are coordinated. is there. It is known that the heteropolyacid salt having such a structure can be partially substituted with a different metal by deleting a part of the skeleton constituent atoms. Such a deficient heteropoly acid salt and a heteropoly acid salt substituted with a different oxidation metal having a lower oxidation number have a negative charge density on the surface, which is higher than that of a normal heteropoly acid salt. It is used as
欠損及び置換ヘテロポリ酸塩の例は数多いが、その多くは酸化触媒として使用されている。例を挙げるとＲｕ置換体によるアルコールの酸化反応が知られている（特許文献１）。 There are many examples of missing and substituted heteropolyacid salts, many of which are used as oxidation catalysts. For example, an oxidation reaction of alcohol by a Ru substituent is known (Patent Document 1).
しかしながら、工業用途として重要で多くの実用化がなされているのは、ヘテロポリアニオンの相手カチオンをＨ+に交換したフリーアシッド型のヘテロポリ酸を用いた酸触媒としての使用である。例えば、テトラヒドロフランの開環重合があげられる（特許文献２）。 However, what is important for industrial use and has been put into practical use is the use as an acid catalyst using a free acid type heteropolyacid obtained by exchanging the cation of the heteropolyanion with H + . For example, ring-opening polymerization of tetrahydrofuran is mentioned (Patent Document 2).
工業用途として有用である酸触媒としてのヘテロポリ酸の例の多くは無置換のフリーアシッド型を用いたものが多い。例えば、Ｈ3［ＰＷ12Ｏ40］、Ｈ3［ＰＭｏ12Ｏ40］、Ｈ4［ＳｉＷ12Ｏ40］、Ｈ4［ＳｉＭｏ12Ｏ40］等があげられる。 Many examples of heteropolyacids as acid catalysts that are useful for industrial applications often use unsubstituted free acid types. For example, H 3 [PW 12 O 40 ], H 3 [PMo 12 O 40], H 4 [SiW 12 O 40], H 4 [SiMo 12 O 40] , and the like.
しかし、これらへテロポリ酸を用いた酸触媒は溶媒に溶解してしまい、回収、再利用が困難であるという問題があった。 However, these acid catalysts using heteropolyacids are dissolved in a solvent, and there is a problem that they are difficult to recover and reuse.
また、フリーアシッド型のヘテロポリ酸はプロトン輸送能に優れるため、塗膜中に含有させて帯電防止剤としての用途が期待されるが、塗膜からブリードアウトしやすく帯電防止性能を維持できないという問題があった。 In addition, since free acid type heteropolyacid has excellent proton transport ability, it is expected to be used as an antistatic agent when it is contained in a coating film, but it is prone to bleed out from the coating film and cannot maintain antistatic performance. was there.
そこで、ヘテロポリ酸をポリマーやシリカなどの担体と混合して物理的に固定化する方法、およびヘテロポリ酸を４級アンモニウム塩型シランカップリング剤に静電荷作用により固定化させる方法が考えられる。 Accordingly, a method of physically immobilizing the heteropolyacid by mixing with a carrier such as a polymer or silica, and a method of immobilizing the heteropolyacid to the quaternary ammonium salt type silane coupling agent by an electrostatic charge effect are conceivable.
しかしながら、物理的に混合させる方法では、十分にブリードアウトを防止することができないという問題があり、静電荷作用により固定化する方法では、より強い電荷を有する化合物により置換されることによってブリードアウトを防止できなくなるという問題があった。 However, there is a problem that the bleed-out cannot be sufficiently prevented by the method of physically mixing, and the bleed-out can be prevented by substitution with a compound having a stronger charge in the method of fixing by electrostatic charge action. There was a problem that it could not be prevented.
そこで、本発明は、担体への固定化が容易な修飾されたフリーアシッド型のヘテロポリ酸、および当該ヘテロポリ酸を用いた固定化修飾フリーアシッド型ヘテロポリ酸を提供することを目的とする。 Accordingly, an object of the present invention is to provide a modified free acid heteropolyacid that can be easily immobilized on a carrier, and an immobilized modified free acid heteropolyacid using the heteropolyacid.
上記課題を解決する本発明の修飾フリーアシッド型ヘテロポリ酸は、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部位に、金属アルコキシドの加水分解物を導入してなるものである。 The modified free acid type heteropolyacid of the present invention that solves the above-mentioned problems is obtained by introducing a hydrolyzate of a metal alkoxide into a deficient site of a heteropoly acid salt in which some of the skeleton constituent atoms are deficient.
また、本発明の修飾フリーアシッド型ヘテロポリ酸は、一般式（１）で示されるものである。
Ｈm[Ｘ（ＹＯＨ）aＯb]・ｎＨ2Ｏ ・・・（１）
[式中、Ｘは骨格構成原子の一部を欠損させたヘテロポリアニオンであり、ＹはＳｉ、Ｔｉ、Ａｌ、Ｚｒから選ばれる何れか１種の原子であり、ｍは１以上の整数であって一般式（１）中の[Ｘ（ＹＯＨ）aＯb]から決定される負電荷の絶対値であり、ｎは１以上の整数である。また、ａは１又は２であり、ｂはａが１のとき０、ａが２のとき１である。]
The modified free acid heteropolyacid of the present invention is represented by the general formula (1).
H m [X (YOH) a O b ] · nH 2 O (1)
[Wherein, X is a heteropolyanion in which a part of the skeleton constituent atoms is missing, Y is any one atom selected from Si, Ti, Al and Zr, and m is an integer of 1 or more. The absolute value of the negative charge determined from [X (YOH) a O b ] in the general formula (1), and n is an integer of 1 or more. A is 1 or 2, b is 0 when a is 1, and 1 when a is 2. ]
また、本発明の固定化修飾フリーアシッド型ヘテロポリ酸は、本発明の修飾フリーアシッド型ヘテロポリ酸を担体に固定化してなるものである。 The immobilized modified free acid heteropolyacid of the present invention is obtained by immobilizing the modified free acid heteropolyacid of the present invention on a carrier.
本発明の修飾フリーアシッド型ヘテロポリ酸は、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部位に金属アルコキシドの加水分解物を導入してなることから、担体との縮合反応により担体に容易に固定化することが可能である。そして、担体に固定化することによって、回収、再利用を容易にできる酸触媒として用いることができるとともに、塗膜からのブリードアウトが起こりにくい帯電防止剤、セパレータからのブリードアウトが起こりにくい燃料電池のセパレータに含有させるプロトン輸送剤として好適に用いることができる。 The modified free acid type heteropolyacid of the present invention is obtained by introducing a hydrolyzate of a metal alkoxide into a deficient site of a heteropoly acid salt in which a part of the skeleton constituent atoms is deficient. It can be easily fixed. And it can be used as an acid catalyst that can be easily recovered and reused by immobilizing it on a carrier, and is an antistatic agent that hardly causes bleed out from the coating film, and a fuel cell that hardly causes bleed out from the separator. It can be suitably used as a proton transfer agent to be contained in the separator.
本発明の固定化修飾フリーアシッド型ヘテロポリ酸は、回収、再利用を容易にできる酸触媒として用いることができるとともに、塗膜からのブリードアウトが起こりにくい帯電防止剤、セパレータからのブリードアウトが起こりにくい燃料電池のセパレータに含有させるプロトン輸送剤として好適に用いることができる。 The immobilization-modified free acid type heteropolyacid of the present invention can be used as an acid catalyst that can be easily recovered and reused, and an antistatic agent that hardly causes bleed-out from a coating film, and bleed-out from a separator occurs. It can be suitably used as a proton transfer agent contained in a separator of a fuel cell that is difficult to use.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
まず、本発明の修飾フリーアシッド型ヘテロポリ酸の実施の形態について説明する。本発明の修飾フリーアシッド型ヘテロポリ酸は、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部位に、金属アルコキシドの加水分解物を導入してなるものである。 First, an embodiment of the modified free acid heteropolyacid of the present invention will be described. The modified free acid type heteropolyacid of the present invention is obtained by introducing a hydrolyzate of a metal alkoxide into a deficient site of a heteropoly acid salt in which a part of the skeleton constituent atoms is deficient.
このような修飾フリーアシッド型ヘテロポリ酸は、骨格構成原子の欠損部分に金属アルコキシドの加水分解物が導入されていることから、当該加水分解物が導入された部分と、これと縮合反応可能な担体とで縮合反応を生じさせることにより、修飾フリーアシッド型ヘテロポリ酸を担体に固定化することができる。 Since such a modified free acid type heteropolyacid has a hydrolyzate of a metal alkoxide introduced into the deficient part of the skeleton constituent atom, the part into which the hydrolyzate has been introduced and a carrier capable of undergoing a condensation reaction therewith The modified free acid type heteropolyacid can be immobilized on the carrier by causing a condensation reaction with.
このような修飾フリーアシッド型ヘテロポリ酸としては、例えば、一般式（１）で示されるものがあげられる。
Ｈm[Ｘ（ＹＯＨ）aＯb]・ｎＨ2Ｏ ・・・（１）
[式中、Ｘは骨格構成原子の一部を欠損させたヘテロポリアニオンであり、ＹはＳｉ、Ｔｉ、Ａｌ、Ｚｒから選ばれる何れか１種の原子であり、ｍは１以上の整数であって一般式（１）中の[Ｘ（ＹＯＨ）aＯb]から決定される負電荷の絶対値であり、ｎは１以上の整数である。また、ａは１又は２であり、ｂはａが１のとき０、ａが２のとき１である。]
Examples of such a modified free acid type heteropolyacid include those represented by the general formula (1).
H m [X (YOH) a O b ] · nH 2 O (1)
[Wherein, X is a heteropolyanion in which a part of the skeleton constituent atoms is missing, Y is any one atom selected from Si, Ti, Al and Zr, and m is an integer of 1 or more. The absolute value of the negative charge determined from [X (YOH) a O b ] in the general formula (1), and n is an integer of 1 or more. A is 1 or 2, b is 0 when a is 1, and 1 when a is 2. ]
一般式（１）中のＸは骨格構成原子の一部を欠損させたヘテロポリアニオンを示す。このようなヘテロポリアニオンとしては、Ｐ2Ｗ17Ｏ61、ＰＷ11Ｏ39、γ−ＰＷ10Ｏ36、ＳｉＷ11Ｏ39、γ−ＳｉＷ10Ｏ36、ＧｅＷ11Ｏ39などがあげられる。 X in the general formula (1) represents a heteropolyanion in which a part of the skeleton constituent atoms is missing. Examples of such heteropolyanions include P 2 W 17 O 61 , PW 11 O 39 , γ-PW 10 O 36 , SiW 11 O 39 , γ-SiW 10 O 36 , and GeW 11 O 39 .
一般式（１）中の（ＹＯＨ）aＯbの部分は、金属アルコキシドの加水分解物を示している。この部分に残存する水酸基が担体との間で縮合反応を起こし、修飾フリーアシッド型ヘテロポリ酸を担体に固定化することができる。（ＹＯＨ）aＯbの部分は具体的には、（ＳｉＯＨ）2Ｏ、（ＴｉＯＨ）、（ＡｌＯＨ）、（ＺｒＯＨ）などがあげられる。これらの中でも、（ＳｉＯＨ）2Ｏは水酸基を二つ有することから、担体との間で縮合反応を起こす際に架橋構造をとることができ、耐擦傷性や耐溶剤性をより向上させることができる点で好ましい。 The part (YOH) a O b in the general formula (1) indicates a hydrolyzate of a metal alkoxide. The hydroxyl group remaining in this part causes a condensation reaction with the carrier, and the modified free acid heteropolyacid can be immobilized on the carrier. Specific examples of the (YOH) a O b portion include (SiOH) 2 O, (TiOH), (AlOH), and (ZrOH). Among these, since (SiOH) 2 O has two hydroxyl groups, it can take a crosslinked structure when causing a condensation reaction with the carrier, which can further improve scratch resistance and solvent resistance. It is preferable in that it can be performed.
また、一般式（１）で示すように、一般式（１）のヘテロポリアニオンの相手カチオンはＨ+となっている。このように相手カチオンをＨ+としたフリーアシッド型のヘテロポリ酸とすることにより、酸触媒としての触媒活性を良好にすることができる。また、フリーアシッド型のヘテロポリ酸は、帯電防止性能に優れた帯電防止剤として用いることができ、さらに、燃料電池のセパレータに含有させることにより、燃料電池のプロトン輸送能を良好にすることができる。 Moreover, as shown by the general formula (1), the partner cation of the heteropolyanion of the general formula (1) is H + . Thus, by using a free acid type heteropolyacid in which the partner cation is H + , the catalytic activity as an acid catalyst can be improved. Further, the free acid type heteropolyacid can be used as an antistatic agent having excellent antistatic performance, and further, by containing it in the separator of the fuel cell, the proton transport ability of the fuel cell can be improved. .
本発明の修飾フリーアシッド型ヘテロポリ酸は、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部位に、金属アルコキシドの加水分解物を導入することにより得ることができる。 The modified free acid type heteropolyacid of the present invention can be obtained by introducing a hydrolyzate of a metal alkoxide into a deficient site of a heteropoly acid salt in which a part of the skeleton constituent atoms is deficient.
具体的には、まず水とアルコール中に金属アルコキシドが溶解した溶液に、別途合成したＫ10［Ｐ2Ｗ17Ｏ61］などのヘテロポリ酸塩の欠損種を化学量論だけ加えて攪拌する。次いで、塩酸で溶液のｐＨを３以下程度に調整する。この作業により、反応系中で金属アルコキシドが加水分解され、当該加水分解物が、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部分に導入される。次いで、得られた溶液を陽イオン交換樹脂が充填されたカラムに通過させることにより、相手カチオンがすべてＨ+に置換され、本発明の修飾フリーアシッド型ヘテロポリ酸を得ることができる。このようにして得られた本発明の修飾フリーアシッド型ヘテロポリ酸は、当該物質の生成を反応系中で確認後溶液状態のまま用いてもよいし、溶媒を除去後固体として用いてもよい。 Specifically, first, a heteropoly acid salt deficient species such as K 10 [P 2 W 17 O 61 ] synthesized separately is added in a stoichiometric amount to a solution in which metal alkoxide is dissolved in water and alcohol. Next, the pH of the solution is adjusted to about 3 or less with hydrochloric acid. By this operation, the metal alkoxide is hydrolyzed in the reaction system, and the hydrolyzate is introduced into the deficient portion of the heteropolyacid salt in which a part of the skeleton constituent atoms are deficient. Next, the resulting solution is passed through a column packed with a cation exchange resin, so that all of the partner cations are replaced with H +, and the modified free acid heteropolyacid of the present invention can be obtained. The modified free acid type heteropolyacid of the present invention thus obtained may be used in a solution state after confirming the production of the substance in the reaction system, or may be used as a solid after removing the solvent.
骨格構成原子の一部を欠損させたヘテロポリ酸塩は、既知文献を参照することにより得ることができる。例えば、Ｒ．Ｃｏｎｔａｎｔ，Ｉｎｏｒｇ．Ｓｙｎｔｈ．，２７，１０４，１９９０．（アメリカ）。 A heteropolyacid salt in which a part of the skeleton constituent atoms is deleted can be obtained by referring to known literature. For example, R.A. Contant, Inorg. Synth. 27, 104, 1990. (America).
このような本発明の修飾フリーアシッド型ヘテロポリ酸は、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部位に、金属アルコキシドの加水分解物を導入してなることから、縮合反応により担体に容易に固定化することが可能である。そして、担体に固定化することにより、回収、再利用が容易な酸触媒、塗膜からのブリードアウトが起こりにくい帯電防止剤、セパレータからのブリードアウトが起こりにくい燃料電池のセパレータに含有させるプロトン輸送剤として用いることができる。 Such a modified free acid type heteropolyacid of the present invention is obtained by introducing a hydrolyzate of a metal alkoxide into a deficient site of a heteropoly acid salt in which a part of the skeleton constituent atoms is deficient. It is possible to immobilize easily. And, by immobilizing on the carrier, acid catalyst that can be easily recovered and reused, antistatic agent that does not easily bleed out from the coating film, and proton transport that is contained in the fuel cell separator that hardly bleed out from the separator. It can be used as an agent.
次に、本発明の固定化修飾フリーアシッド型ヘテロポリ酸の実施の形態について説明する。本発明の固定化修飾フリーアシッド型ヘテロポリ酸は、上述した本発明の修飾フリーアシッド型ヘテロポリ酸を担体に固定化してなることを特徴とするものである。 Next, an embodiment of the immobilization modified free acid type heteropolyacid of the present invention will be described. The immobilization modified free acid type heteropolyacid of the present invention is characterized by immobilizing the aforementioned modified free acid type heteropolyacid of the present invention on a carrier.
本発明の修飾フリーアシッド型ヘテロポリ酸を担体に固定化するには、当該ヘテロポリ酸の加水分解物が導入された部分と担体との間で縮合反応を生じさせればよい。なお、担体への固定化は最終的になされていればよい。したがって、塗膜やセパレータに含ませる時点では担体に固定化されていなくても、その後塗膜やセパレータに含まれる担体との反応が進み固定化されればよい。 In order to immobilize the modified free acid type heteropolyacid of the present invention on a carrier, a condensation reaction may be caused between the portion into which the hydrolyzate of the heteropolyacid is introduced and the carrier. It should be noted that the immobilization on the carrier may be finally performed. Therefore, even if it is not immobilized on the carrier at the time of inclusion in the coating film or the separator, the reaction with the carrier contained in the coating film or the separator may proceed and then be immobilized.
図１は、骨格構成原子の一部を欠損させたヘテロポリ酸塩の欠損部位に、金属アルコキシドであるテトラエトキシシランの加水分解物を導入してなる本発明の修飾フリーアシッド型ヘテロポリ酸が、担体であるシリカに固定化された状態のイメージを簡易的に示す図である。図１中において、Ａはヘテロポリアニオン、Ｂは担体、Ｓｉはケイ素原子、Ｏは酸素原子、Ｗはタングステン原子を示す。図１に示すように、Ｓｉ−Ｏ−Ｓｉ結合により、フリーアシッド型ヘテロポリ酸が担体に固定化されていると考えられる。 FIG. 1 shows a modified free acid heteropolyacid of the present invention in which a hydrolyzate of tetraethoxysilane, which is a metal alkoxide, is introduced into a deficient site of a heteropoly acid salt in which a part of the skeleton constituent atoms is deficient. It is a figure which shows simply the image of the state fixed to the silica which is. In FIG. 1, A represents a heteropolyanion, B represents a carrier, Si represents a silicon atom, O represents an oxygen atom, and W represents a tungsten atom. As shown in FIG. 1, it is considered that the free acid type heteropolyacid is immobilized on the carrier by Si—O—Si bonds.
上記縮合反応は、修飾フリーアシッド型ヘテロポリ酸とこれと縮合反応可能な担体とを混合すれば常温でも反応が進行するが、室温〜７０℃程度に加熱することで反応速度を速めることができる。反応時間は、加熱下で２〜２４時間程度である。 The above condensation reaction proceeds at room temperature if a modified free acid heteropolyacid and a carrier capable of condensation reaction are mixed, but the reaction rate can be increased by heating to about room temperature to 70 ° C. The reaction time is about 2 to 24 hours under heating.
担体としては、修飾フリーアシッド型ヘテロポリ酸の金属アルコキシドの加水分解物が導入された部分と縮合反応が可能なものが用いられる。このような担体としては、シリカ、酸化チタン、アルミナ、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、珪酸アルミニウム、ガラスなどの無機物、ジメチルジメトキシシラン、メチルフェニジメトキシシランなどの多官能アルコキシシランおよびその加水分解物、その他の多官能金属アルコキシドおよびその加水分解物、水酸基及び／又はアルコキシ基を有するシリコーン樹脂などがあげられる。担体の種類は用途に応じて使い分けることができるが、安定性、汎用性の観点からシリカが好ましい。また、固定化修飾フリーアシッド型ヘテロポリ酸を燃料電池のセパレータとして用いる場合には、柔軟性および耐溶剤性に優れるという観点から、２官能又は３官能アルコキシシラン、水酸基及び／又はアルコキシ基を有するシリコーン樹脂を担体とすることが好ましい。 As the carrier, a carrier that can undergo a condensation reaction with a portion into which a hydrolyzate of a metal alkoxide of a modified free acid heteropolyacid has been introduced. Examples of such carriers include silica, titanium oxide, alumina, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, inorganic materials such as glass, polyfunctional alkoxysilanes such as dimethyldimethoxysilane and methylphenidimethoxysilane, and hydrolysates thereof. And other polyfunctional metal alkoxides and hydrolysates thereof, and silicone resins having a hydroxyl group and / or an alkoxy group. Although the kind of support | carrier can be used properly according to a use, a silica is preferable from a viewpoint of stability and versatility. In addition, when the immobilization modified free acid type heteropolyacid is used as a fuel cell separator, a silicone having a bifunctional or trifunctional alkoxysilane, a hydroxyl group and / or an alkoxy group from the viewpoint of excellent flexibility and solvent resistance. It is preferable to use a resin as a carrier.
なお、多官能アルコキシシランおよびその加水分解物、その他の多官能金属アルコキシドおよびその加水分解物を担体として用いる場合には、担体に修飾フリーアシッド型ヘテロポリ酸が固定化された状態はゾルの状態である。したがって、（多官能アルコキシシランその他の金属アルコキシドの加水分解が完了していない場合は加水分解を完了させた後）加熱によりゾル溶液を乾燥、脱水縮合して用いることが好ましい。 When polyfunctional alkoxysilane and its hydrolyzate and other polyfunctional metal alkoxide and its hydrolyzate are used as a carrier, the state where the modified free acid type heteropolyacid is immobilized on the carrier is a sol state. is there. Accordingly, it is preferable to use the sol solution after drying and dehydrating condensation by heating (after completion of hydrolysis if the hydrolysis of the polyfunctional alkoxysilane or other metal alkoxide is not completed).
担体の形状は用途に応じて使い分けることができる。酸触媒として用いる場合には、取り扱い性に優れる微粒子状であることが好ましい。この場合、微粒子の平均粒子径は、０．１〜１００μｍであることが好ましい。平均粒子径をこのような範囲とすることにより、固定化の際の縮合反応を進みやすくできるとともに、取り扱い性を向上させることができる。 The shape of the carrier can be properly used according to the application. When used as an acid catalyst, it is preferably in the form of fine particles having excellent handleability. In this case, the average particle diameter of the fine particles is preferably 0.1 to 100 μm. By setting the average particle diameter in such a range, it is possible to facilitate the condensation reaction during immobilization and improve the handleability.
このような本発明の固定化修飾フリーアシッド型ヘテロポリ酸は、回収、再利用が容易な酸触媒として用いることができる。触媒反応としては、各種化合物のエステル化反応、アルキル化反応、アシル化反応の他、アルケンの水和反応、アルケンの酸化反応などがあげられる。さらに、本発明の固定化修飾フリーアシッド型ヘテロポリ酸は、塗膜からのブリードアウトが起こりにくい帯電防止剤、セパレータからのブリードアウトが起こりにくい燃料電池のセパレータに含有させるプロトン輸送剤として用いることができる。また、担体の種類にもよるが、殆どの成分が無機物であるため、耐薬品性や耐熱性に極めて優れており、上述した用途に用いる際に薬品や熱により劣化することもない。 Such an immobilization-modified free acid heteropolyacid of the present invention can be used as an acid catalyst that can be easily recovered and reused. Examples of the catalytic reaction include esterification reaction, alkylation reaction, acylation reaction of various compounds, alkene hydration reaction, alkene oxidation reaction, and the like. Furthermore, the immobilization-modified free acid type heteropolyacid of the present invention can be used as an antistatic agent that hardly causes bleed-out from a coating film, and a proton transport agent that is contained in a fuel cell separator that hardly causes bleed-out from a separator. it can. Although depending on the type of carrier, since most of the components are inorganic, they are extremely excellent in chemical resistance and heat resistance, and are not deteriorated by chemicals or heat when used in the above-mentioned applications.
以下、実施例により本発明を更に説明する。なお、「部」、「％」は特に示さない限り、重量基準とする。 The following examples further illustrate the present invention. “Parts” and “%” are based on weight unless otherwise specified.
［実施例１］
１．修飾物製造工程
（１）ヘテロポリ酸塩の欠損部位への加水分解物の導入、イオン交換
テトラエトキシシラン０．４２ｇ（２ｍｍｏｌ）をＨ2Ｏ／ＥｔＯＨ＝５０／５０ｍＬの混合溶媒に溶解させた。５分間攪拌後、文献（Ｒ．Ｃｏｎｔａｎｔ，Ｉｎｏｒｇ．Ｓｙｎｔｈ．，２７，１０４，１９９０）に従い合成した一欠損Ｄａｗｓｏｎ型タングストポリ酸塩Ｋ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏを５．０ｇ（１ｍｍｏｌ）加えてしばらく攪拌した。次いで、１Ｍ塩酸を用いて溶液のｐＨを１．８に調整して３０分間攪拌した。このとき反応溶液は白色懸濁から淡黄色懸濁液に変化した。次いで、不溶物をろ過により取り除いた溶液をＨ+でチャージされたイオン交換樹脂（アンバーライト120NBA：ローム・アンド・ハース社）に通薬した。使用したイオン交換樹脂の量は１００ｍＬ、通薬速度はＳＶ４とした。次いで、通薬後の溶液をナスフラスコに移しロータリーエバポレーターを使用して溶媒を取り除き、黄色粉体の化合物ａを得た。次いで、析出した粉体を回収して一晩真空乾燥した。得られた化合物ａの収量は３．１８ｇであった。
[Example 1]
1. Modified product production process (1) Introduction of hydrolyzate to deficient site of heteropolyacid salt, ion exchange Tetraethoxysilane 0.42 g (2 mmol) was dissolved in a mixed solvent of H 2 O / EtOH = 50/50 mL. After stirring for 5 minutes, 5.0 g of one-deficient Dawson-type Tungstopolyacid salt K 10 [P 2 W 17 O 61 ] · 19H 2 O synthesized according to the literature (R. Constant, Inorg. Synth., 27, 104, 1990) was used. (1 mmol) was added and stirred for a while. Subsequently, the pH of the solution was adjusted to 1.8 using 1M hydrochloric acid, and stirred for 30 minutes. At this time, the reaction solution changed from a white suspension to a pale yellow suspension. Next, the solution from which insolubles were removed by filtration was passed through an ion exchange resin (Amberlite 120NBA: Rohm and Haas) charged with H + . The amount of ion exchange resin used was 100 mL, and the drug delivery rate was SV4. Next, the solution after passing the medicine was transferred to an eggplant flask and the solvent was removed using a rotary evaporator to obtain a yellow powder of compound a. Next, the precipitated powder was recovered and vacuum-dried overnight. The yield of Compound a thus obtained was 3.18 g.
（２）構造解析
得られた化合物ａについてＦＴ−ＩＲおよびＮＭＲの測定を行った。結果を以下に示す。
＜ＦＴ−ＩＲ（ＡＴＲ法）＞
３３８１ｍ，２１１３ｗ，１６１２ｍ，１０８３ｓ，９５３ｓ，９０３ｓ，６８４ｓ ｃｍ-1
＜31Ｐ ＮＭＲ＞
（１９．９℃、Ｄ2Ｏ）：δ−１０．０，−１３．２ｐｐｍ
(2) Structural analysis The obtained compound a was subjected to FT-IR and NMR measurements. The results are shown below.
<FT-IR (ATR method)>
3381m, 2113w, 1612m, 1083s, 953s, 903s, 684s cm -1
<31 P NMR>
(19.9 ° C., D 2 O): δ-10.0, -13.2 ppm
以上の分析結果から、化合物ａは、骨格構成原子の一部を欠損させたヘテロポリ酸塩であるＫ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏの欠損部位に、金属アルコキシドであるテトラエトキシシランの加水分解物が導入されてなる修飾フリーアシッド型へテロポリ酸、Ｈ6[Ｐ2Ｗ17Ｏ61（ＳｉＯＨ）2Ｏ]の水和物であること、およびこの修飾フリーアシッド型ヘテロポリ酸の構造を保つ単一種として得られていることが確認された。こうして実施例１の修飾フリーアシッド型ヘテロポリ酸（化合物ａ）を得た。 From the above analysis results, compound a is tetraethoxy which is a metal alkoxide at the deficient site of K 10 [P 2 W 17 O 61 ] · 19H 2 O, which is a heteropoly acid salt in which a part of the skeleton constituent atoms is missing. A modified free acid type heteropolyacid having a silane hydrolyzate introduced therein, being a hydrate of H 6 [P 2 W 17 O 61 (SiOH) 2 O], and of the modified free acid type heteropolyacid It was confirmed that it was obtained as a single species that maintained the structure. In this way, the modified free acid type heteropolyacid (compound a) of Example 1 was obtained.
２．シリカ薄膜の形成
テトラエトキシシラン５．０部、水２．５部、エタノール５．１部、実施例１の修飾フリーアシッド型ヘテロポリ酸（化合物ａ）１．５部からなる混合液を、２５℃で２４時間攪拌してテトラエトキシシランを加水分解し、母液Ａを得た。この段階で担体となるテトラエトキシシランの加水分解物と、実施例１の修飾フリーアシッド型ヘテロポリ酸との間で縮合反応が生じ、実施例１の修飾フリーアシッド型ヘテロポリ酸が担体に固定化された状態となっている。
2. Formation of Silica Thin Film A mixed solution consisting of 5.0 parts of tetraethoxysilane, 2.5 parts of water, 5.1 parts of ethanol, and 1.5 parts of the modified free acid type heteropolyacid (compound a) of Example 1 was prepared at 25 ° C. Was stirred for 24 hours to hydrolyze tetraethoxysilane to obtain mother liquor A. At this stage, a condensation reaction occurs between the hydrolyzate of tetraethoxysilane serving as a carrier and the modified free acid heteropolyacid of Example 1, and the modified free acid heteropolyacid of Example 1 is immobilized on the carrier. It is in the state.
次いで、５．０部の母液Ａに対し、イソプロピルアルコール、ｎ−ブタノール、シクロヘキサノンをそれぞれ４．０部、５．０部、１．０部添加して希釈し、希釈液Ａ’を得た。次いで、厚み１００μｍのポリエステルフィルム上に、希釈液Ａ’をバーコーター法で塗布し、１００℃で３分間加熱して、加水分解物を脱水縮合してシリカ薄膜を形成し、実施例１の透明導電性シートを得た。 Next, 4.0 parts, 5.0 parts, and 1.0 parts of isopropyl alcohol, n-butanol, and cyclohexanone were added to 5.0 parts of mother liquor A, respectively, to obtain a diluted solution A ′. Next, on the polyester film having a thickness of 100 μm, the diluent A ′ was applied by a bar coater method, heated at 100 ° C. for 3 minutes, and the hydrolyzate was dehydrated and condensed to form a silica thin film. A conductive sheet was obtained.
実施例１で得られた透明導電性シートを用い、ＪＩＳ Ｋ６９１１：１９９５に基づき、透明導電性シートの表面抵抗を測定し表面抵抗率を算出した。測定は、透明導電性シートを水に浸漬していないもの、水に１時間浸漬後のもの、１５時間浸漬後のもの、６０時間浸漬後のものについて行った。測定結果は、順に、３．９×１０8Ω／□、４．９×１０8Ω／□、５．３×１０8Ω／□、６．６×１０8Ω／□であった。 Using the transparent conductive sheet obtained in Example 1, the surface resistance of the transparent conductive sheet was measured and the surface resistivity was calculated based on JIS K6911: 1995. The measurement was performed on the transparent conductive sheet not immersed in water, the one after 1 hour immersion in water, the one after 15 hours immersion, and the one after 60 hours immersion. The measurement results were 3.9 × 10 8 Ω / □, 4.9 × 10 8 Ω / □, 5.3 × 10 8 Ω / □, and 6.6 × 10 8 Ω / □, respectively.
［実施例２］
１．修飾物製造工程
（１）ヘテロポリ酸塩の欠損部位への加水分解物の導入、イオン交換
Ａｌ（ＯＥｔ）3 ０．１６２ｇ（１ｍｍｏｌ）を純水４０ｍＬに分散させ、１Ｍ塩酸を用いて溶液のｐＨを１．５に調整した。得られた無色透明溶液に、実施例１と同様の一欠損Ｄａｗｓｏｎ型タングストポリ酸塩Ｋ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏを５．０ｇ（１ｍｍｏｌ）加えて１時間攪拌した。ひだ折ろ紙を用いて未反応のポリ酸塩を除去後、過剰量のＭｅ2ＮＨ2Ｃｌ ５．５ｇ（６７．５ｍｍｏｌ）を加えて白色粉体を得た。
[Example 2]
1. Modified product production process (1) Introduction of hydrolyzate to deficient site of heteropoly acid salt, ion exchange 0.162 g (1 mmol) of Al (OEt) 3 is dispersed in 40 mL of pure water, and the pH of the solution using 1M hydrochloric acid. Was adjusted to 1.5. To the obtained colorless and transparent solution, 5.0 g (1 mmol) of one-deficient Dawson-type Tungstopolyacid salt K 10 [P 2 W 17 O 61 ] · 19H 2 O as in Example 1 was added and stirred for 1 hour. After removing the unreacted polyacid salt using a pleated filter paper, an excessive amount of 5.5 g (67.5 mmol) of Me 2 NH 2 Cl was added to obtain a white powder.
得られた粉体をエタノール、ジエチルエーテルで洗浄後充分吸引乾燥させた。この粉体３．０ｇを純水５ｍＬに分散させ、実施例１と同様のイオン交換樹脂５ｇを加えてカチオン交換した。ろ過によりイオン交換樹脂を取り除き得られたろ液に再び実施例１と同様のイオン交換樹脂を５ｇ添加した。次いで、イオン交換樹脂をろ別した後、得られた淡黄色溶液を凍結乾燥させて、化合物ｂを得た。化合物ｂの収量は２．３ｇであった。 The obtained powder was washed with ethanol and diethyl ether and then sufficiently sucked and dried. 3.0 g of this powder was dispersed in 5 mL of pure water, and 5 g of the same ion exchange resin as in Example 1 was added to perform cation exchange. 5 g of the same ion exchange resin as in Example 1 was again added to the filtrate obtained by removing the ion exchange resin by filtration. Subsequently, after ion-exchange resin was separated by filtration, the obtained pale yellow solution was freeze-dried to obtain Compound b. The yield of compound b was 2.3 g.
（２）構造解析
得られた化合物ｂについてＦＴ−ＩＲおよびＮＭＲの測定を行った。結果を以下に示す。
＜ＦＴ−ＩＲ（ＡＴＲ法）＞
１０９５ｍ，９６６ｍ，８９９ｍ，７３５ｍ ｃｍ-1
＜31Ｐ ＮＭＲ＞
（１９．２℃、Ｄ2Ｏ）：δ−１０．５，−１３．１ｐｐｍ
(2) Structural analysis The obtained compound b was subjected to FT-IR and NMR measurements. The results are shown below.
<FT-IR (ATR method)>
1095m, 966m, 899m, 735m cm -1
<31 P NMR>
(19.2 ° C., D 2 O): δ-10.5, -13.1 ppm
以上の分析結果から、化合物ｂは、骨格構成原子の一部を欠損させたヘテロポリ酸塩であるＫ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏの欠損部位に、金属アルコキシドであるＡｌ（ＯＥｔ）3の加水分解物が導入されてなる修飾フリーアシッド型へテロポリ酸Ｈ8［Ｐ2Ｗ17Ｏ61（ＡｌＯＨ）］の水和物であること、およびこの修飾フリーアシッド型ヘテロポリ酸の構造を保つ単一種として得られていることが確認された。こうして実施例２の修飾フリーアシッド型ヘテロポリ酸（化合物ｂ）を得た。 From the above analysis results, compound b has a metal alkoxide, Al (, which is a deficient site of K 10 [P 2 W 17 O 61 ] · 19H 2 O, which is a heteropolyacid salt in which a part of the skeleton constituent atoms are missing. OEt) 3 hydrolyzate of modified free acid type heteropolyacid H 8 [P 2 W 17 O 61 (AlOH)], and structure of this modified free acid type heteropolyacid It was confirmed that it was obtained as a single species that preserved Thus, a modified free acid type heteropolyacid (compound b) of Example 2 was obtained.
［実施例３］
１．修飾物製造工程
（１）ヘテロポリ酸塩の欠損部位への加水分解物の導入、イオン交換
Ｓｉ（ＯＥｔ）4 ０．１４ｇ（０．６ｍｍｏｌ）を純水／エタノール＝１２／６ｍＬの混合溶媒に溶解させた。５分間攪拌後、実施例１と同様の文献に従い合成した一欠損Ｋｅｇｇｉｎ型タングストポリ酸塩Ｋ7［ＰＷ11Ｏ39]・１２Ｈ2Ｏを１．０ｇ（０．３ｍｍｏｌ）加えてしばらく攪拌した。次いで、１Ｍ塩酸を用いて溶液のｐＨを１．５に調整し３０分間攪拌した。次に、実施例１と同様のイオン交換樹脂２０ｇを加えてゆっくりと攪拌した。次いで、イオン交換樹脂をろ別した後、ナスフラスコに移しロータリーエバポレーターを使用してエタノールを取り除き、残った水を凍結乾燥により除去し黄色粉体の化合物ｃを得た。化合物ｃの収量は０．６４ｇであった。
[Example 3]
1. Modified product production process (1) Introduction of hydrolyzate to deficient site of heteropoly acid salt, ion exchange 0.14 g (0.6 mmol) of Si (OEt) 4 is dissolved in a mixed solvent of pure water / ethanol = 12/6 mL I let you. After stirring for 5 minutes, 1.0 g (0.3 mmol) of one-deficient Keggin-type tungstopolyacid salt K 7 [PW 11 O 39 ] · 12H 2 O synthesized according to the same literature as in Example 1 was added and stirred for a while. Then, the pH of the solution was adjusted to 1.5 using 1M hydrochloric acid, and stirred for 30 minutes. Next, the same ion exchange resin 20g as Example 1 was added, and it stirred slowly. Subsequently, the ion exchange resin was filtered off, transferred to an eggplant flask, ethanol was removed using a rotary evaporator, and the remaining water was removed by lyophilization to obtain a yellow powder of compound c. The yield of compound c was 0.64 g.
（２）構造解析
得られた化合物ｃについてＦＴ−ＩＲおよびＮＭＲの測定を行った。結果を以下に示す。
＜ＦＴ−ＩＲ（ＡＴＲ法）＞
１０７７ｍ，９７０ｍ，８８３ｍ，７０７ｓ ｃｍ-1
＜31Ｐ ＮＭＲ＞
（１８．９℃、Ｄ2Ｏ）：δ−１３．７ｐｐｍ
(2) Structural analysis The obtained compound c was subjected to FT-IR and NMR measurements. The results are shown below.
<FT-IR (ATR method)>
1077m, 970m, 883m, 707s cm -1
<31 P NMR>
(18.9 ° C., D 2 O): δ-13.7 ppm
以上の分析結果から、化合物ｃは、骨格構成原子の一部を欠損させたヘテロポリ酸塩であるＫ7［ＰＷ11Ｏ39]・１２Ｈ2Ｏの欠損部位に、金属アルコキシドであるＳｉ（ＯＥｔ）4 の加水分解物が導入されてなる修飾フリーアシッド型へテロポリ酸Ｈ3[ＰＷ11Ｏ39（ＳｉＯＨ）2Ｏ]の水和物であること、およびこの修飾フリーアシッド型ヘテロポリ酸の構造を保つ単一種として得られていることが確認された。こうして実施例３の修飾フリーアシッド型ヘテロポリ酸（化合物ｃ）を得た。 From the above analysis results, compound c is a metal alkoxide, Si (OEt), at the deficient portion of K 7 [PW 11 O 39 ] · 12H 2 O, which is a heteropolyacid salt in which a part of the skeleton constituent atoms is missing. 4 is a hydrate of a modified free acid type heteropolyacid H 3 [PW 11 O 39 (SiOH) 2 O] obtained by introducing a hydrolyzate of 4 and maintains the structure of this modified free acid type heteropolyacid It was confirmed that it was obtained as a single species. In this way, the modified free acid type heteropolyacid (compound c) of Example 3 was obtained.
［実施例４］
１．修飾物製造工程
（１）ヘテロポリ酸塩の欠損部位への加水分解物の導入、イオン交換
Ａｌ（ＯＥｔ）2０．０５ｇ（０．３ｍｍｏｌ）を純水／エタノール＝１２／６ｍＬの混合溶媒に分散させた。５分間攪拌後、実施例３と同様の一欠損Ｋｅｇｇｉｎ型タングストポリ酸塩Ｋ7［ＰＷ11Ｏ39]・１２Ｈ2Ｏを１．０ｇ（０．３ｍｍｏｌ）加えてしばらく攪拌した。次いで、１Ｍ塩酸を用いて溶液のｐＨを１．５に調整し３０分間攪拌した。次に、実施例１と同様のイオン交換樹脂２０ｇを加えてゆっくりと攪拌した。次いで、イオン交換樹脂をろ別した後、ナスフラスコに移しロータリーエバポレーターを使用してエタノールを取り除き、残った水を凍結乾燥により除去し黄色粉体の化合物ｄを得た。化合物ｄの収量は０．６５ｇであった。
[Example 4]
1. Modified product production process (1) Introduction of hydrolyzate to deficient site of heteropolyacid salt, ion exchange Disperse 0.05 g (0.3 mmol) of Al (OEt) 2 in a mixed solvent of pure water / ethanol = 12/6 mL I let you. After stirring for 5 minutes, 1.0 g (0.3 mmol) of one-deficient Keggin-type tungstopolyacid salt K 7 [PW 11 O 39 ] · 12H 2 O as in Example 3 was added and stirred for a while. Then, the pH of the solution was adjusted to 1.5 using 1M hydrochloric acid, and stirred for 30 minutes. Next, the same ion exchange resin 20g as Example 1 was added, and it stirred slowly. Subsequently, the ion exchange resin was filtered off, transferred to an eggplant flask, ethanol was removed using a rotary evaporator, and the remaining water was removed by lyophilization to obtain a yellow powder of compound d. The yield of compound d was 0.65 g.
（２）構造解析
得られた化合物ｄについてＦＴ−ＩＲおよびＮＭＲの測定を行った。結果を以下に示す。
＜ＦＴ−ＩＲ（ＡＴＲ法）＞
１０７９ｍ，１０３４ｗ，９７８ｍ，８８７ｍ，７２０ｓ ｃｍ-1
＜31Ｐ ＮＭＲ＞
（１８．６℃、Ｄ2Ｏ）：δ−１３．７ｐｐｍ
(2) Structural analysis The obtained compound d was subjected to FT-IR and NMR measurements. The results are shown below.
<FT-IR (ATR method)>
1079m, 1034w, 978m, 887m, 720s cm -1
<31 P NMR>
(18.6 ° C., D 2 O): δ-13.7 ppm
以上の分析結果から、化合物ｄは、骨格構成原子の一部を欠損させたヘテロポリ酸塩であるＫ7［ＰＷ11Ｏ39]・１２Ｈ2Ｏの欠損部位に、金属アルコキシドであるＡｌ（ＯＥｔ）2 の加水分解物が導入されてなる修飾フリーアシッド型へテロポリ酸Ｈ5[ＰＷ11Ｏ39（ＡｌＯＨ）]の水和物であること、およびこの修飾フリーアシッド型ヘテロポリ酸の構造を保つ単一種として得られていることが確認された。こうして実施例４の修飾フリーアシッド型ヘテロポリ酸（化合物ｄ）を得た。 From the above analysis results, compound d is Al (OEt) which is a metal alkoxide at the deficient site of K 7 [PW 11 O 39 ] · 12H 2 O, which is a heteropolyacid salt in which a part of the skeleton constituent atoms is missing. A hydrolyzate of a modified free acid type heteropolyacid H 5 [PW 11 O 39 (AlOH)] obtained by introducing a hydrolyzate of 2 and a single species that maintains the structure of the modified free acid type heteropolyacid It was confirmed that it was obtained as Thus, a modified free acid type heteropolyacid (compound d) of Example 4 was obtained.
［実施例５］
１．修飾物製造工程
（１）ヘテロポリ酸塩の欠損部位への加水分解物の導入、イオン交換
実施例１と同様の一欠損Ｄａｗｓｏｎ型タングストポリ酸塩Ｋ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏを２．３ｇ（０．５ｍｍｏｌ）を純水２０ｍＬに分散し、１Ｍ塩酸を用いて溶液のｐＨを１．８に調整した（無色透明溶液）。別途Ｚｒ（ＯＢｕ）4０．１９ｇ（０．５ｍｍｏｌ）をｎ−プロパノールに溶解したものを前記無色透明溶液に加えて１時間攪拌した。生成した白色粉体をひだ折ろ紙を用いて除去した溶液にＭｅ2ＮＨ2Ｃｌ ６．５２ｇ（８０ｍｍｏｌ）を加え白色粉体を得た。
[Example 5]
1. Modified product production process (1) Introduction of hydrolyzate to deficient site of heteropolyacid salt, ion exchange One deficient Dawson type Tungstopolyacid salt K 10 [P 2 W 17 O 61 ] · 19H 2 O as in Example 1 2.3 g (0.5 mmol) was dispersed in 20 mL of pure water, and the pH of the solution was adjusted to 1.8 using 1 M hydrochloric acid (colorless transparent solution). Separately, 0.19 g (0.5 mmol) of Zr (OBu) 4 dissolved in n-propanol was added to the colorless transparent solution and stirred for 1 hour. 6.52 g (80 mmol) of Me 2 NH 2 Cl was added to a solution obtained by removing the produced white powder using fold-fold filter paper to obtain a white powder.
生成した白色粉体をメンブランフィルターで回収後エタノール、ジエチルエーテルで洗浄した。この粉体０．５ｇを純水５ｍＬに分散させ、実施例１と同様のイオン交換樹脂５ｇを加えてカチオン交換した。ろ過によりイオン交換樹脂を取り除き得られたろ液に再び実施例１と同様のイオン交換樹脂を５ｇ添加した。次いで、イオン交換樹脂をろ別した後、得られた淡黄色溶液を凍結乾燥させて、化合物ｅを得た。化合物ｅの収量は０．３ｇであった。 The produced white powder was recovered with a membrane filter and then washed with ethanol and diethyl ether. 0.5 g of this powder was dispersed in 5 mL of pure water, and 5 g of the same ion exchange resin as in Example 1 was added to perform cation exchange. 5 g of the same ion exchange resin as in Example 1 was again added to the filtrate obtained by removing the ion exchange resin by filtration. Then, after ion-exchange resin was filtered off, the resulting pale yellow solution was lyophilized to obtain compound e. The yield of compound e was 0.3 g.
（２）構造解析
得られた化合物ｅについてＦＴ−ＩＲおよびＮＭＲの測定を行った。結果を以下に示す。
＜ＦＴ−ＩＲ（ＡＴＲ法）＞
１０８２ｍ，１０１５ｗ，９４５ｍ，９０７ｍ，７４３ｍ ｃｍ-1
＜31Ｐ ＮＭＲ＞
（１９．２℃、Ｄ2Ｏ）：δ−９．９７，−１３．７ｐｐｍ
(2) Structural analysis The obtained compound e was subjected to FT-IR and NMR measurements. The results are shown below.
<FT-IR (ATR method)>
1082m, 1015w, 945m, 907m, 743m cm -1
<31 P NMR>
(19.2 ° C., D 2 O): δ-9.97, −13.7 ppm
以上の分析結果から、化合物ｅは、骨格構成原子の一部を欠損させたヘテロポリ酸塩であるＫ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏの欠損部位に、金属アルコキシドであるＺｒ（ＯＢｕ）4の加水分解物が導入されてなる修飾フリーアシッド型へテロポリ酸Ｈ7[Ｐ2Ｗ17Ｏ61（ＺｒＯＨ）]の水和物であること、およびこの修飾フリーアシッド型ヘテロポリ酸の構造を保つ単一種として得られていることが確認された。こうして実施例５の修飾フリーアシッド型ヘテロポリ酸（化合物ｅ）を得た。 From the above analysis results, compound e has a metal alkoxide, Zr (), at the deficient site of K 10 [P 2 W 17 O 61 ] · 19H 2 O, which is a heteropolyacid salt in which a part of the skeleton constituent atoms is missing. OBu) 4 hydrolyzate of modified free acid type heteropolyacid H 7 [P 2 W 17 O 61 (ZrOH)], and the structure of this modified free acid type heteropolyacid It was confirmed that it was obtained as a single species that preserved In this way, the modified free acid type heteropolyacid (compound e) of Example 5 was obtained.
［実施例６］
１．修飾物製造工程
（１）ヘテロポリ酸塩の欠損部位への加水分解物の導入、イオン交換
実施例１と同様の一欠損Ｄａｗｓｏｎ型タングストポリ酸塩Ｋ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏを２．３ｇ（０．５ｍｍｏｌ）を純水２０ｍＬに分散し、１Ｍ塩酸を用いて溶液のｐＨを１．８に調整した（無色透明溶液）。別途Ｔｉ（Ｏ−ｉ−Ｐｒ）4０．１４ｇ（０．５ｍｍｏｌ）をｎ−プロパノールに溶解したものを前記無色透明溶液に加えて１時間攪拌した。生成した白色粉体をひだ折ろ紙を用いて除去しＭｅ2ＮＨ2Ｃｌ ３．２６ｇ（４０ｍｍｏｌ）を加え白色粉体を得た。
[Example 6]
1. Modified product production process (1) Introduction of hydrolyzate to deficient site of heteropolyacid salt, ion exchange One deficient Dawson type Tungstopolyacid salt K 10 [P 2 W 17 O 61 ] · 19H 2 O as in Example 1 2.3 g (0.5 mmol) was dispersed in 20 mL of pure water, and the pH of the solution was adjusted to 1.8 using 1 M hydrochloric acid (colorless transparent solution). Separately, 0.14 g (0.5 mmol) of Ti (Oi-Pr) 4 dissolved in n-propanol was added to the colorless transparent solution and stirred for 1 hour. The produced white powder was removed using a fold filter paper, and 3.26 g (40 mmol) of Me 2 NH 2 Cl was added to obtain a white powder.
生成した白色粉体をメンブランフィルターで回収後エタノール、ジエチルエーテルで洗浄した。この粉体１．５ｇを純水５ｍＬに分散させ、実施例１と同様のイオン交換樹脂５ｇを加えてカチオン交換した。ろ過によりイオン交換樹脂を取り除き得られたろ液に再び実施例１と同様のイオン交換樹脂を５ｇ添加した。次いで、イオン交換樹脂をろ別した後、得られた淡黄色溶液を凍結乾燥させて、化合物ｆを得た。化合物ｆの収量は０．６ｇであった。 The produced white powder was recovered with a membrane filter and then washed with ethanol and diethyl ether. 1.5 g of this powder was dispersed in 5 mL of pure water, and 5 g of the same ion exchange resin as in Example 1 was added to perform cation exchange. 5 g of the same ion exchange resin as in Example 1 was again added to the filtrate obtained by removing the ion exchange resin by filtration. Then, after ion-exchange resin was filtered off, the resulting pale yellow solution was lyophilized to obtain compound f. The yield of compound f was 0.6 g.
（２）構造解析
得られた化合物ｆについてＦＴ−ＩＲおよびＮＭＲの測定を行った。結果を以下に示す。
＜ＦＴ−ＩＲ（ＡＴＲ法）＞
１０８５ｍ，１０１６ｗ，９４９ｍ，９１２ｍ，７５１ｍ ｃｍ-1
＜31Ｐ ＮＭＲ＞
（１９．２℃、Ｄ2Ｏ）：δ−１０．６，−１３．７ ｐｐｍ
(2) Structural analysis The obtained compound f was subjected to FT-IR and NMR measurements. The results are shown below.
<FT-IR (ATR method)>
1085m, 1016w, 949m, 912m, 751m cm -1
<31 P NMR>
(19.2 ° C., D 2 O): δ-10.6, -13.7 ppm
以上の分析結果から、化合物ｆは、骨格構成原子の一部を欠損させたヘテロポリ酸塩であるＫ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏの欠損部位に、金属アルコキシドであるＴｉ（Ｏ−ｉ−Ｐｒ）4の加水分解物が導入されてなる修飾フリーアシッド型へテロポリ酸Ｈ7[Ｐ2Ｗ17Ｏ61（ＴｉＯＨ）]の水和物であること、およびこの修飾フリーアシッド型ヘテロポリ酸の構造を保つ単一種として得られていることが確認された。こうして実施例６の修飾フリーアシッド型ヘテロポリ酸（化合物ｆ）を得た。 From the above analysis results, the compound f has a metal alkoxide Ti (at the deficient site of K 10 [P 2 W 17 O 61 ] · 19H 2 O, which is a heteropoly acid salt in which a part of the skeleton constituent atoms are missing. O-i-Pr) be the hydrate of 4 heteropolyacid acid H 7 hydrolyzate to modified free acid type has been introduced [P 2 W 17 O 61 ( TiOH)], and the modified free acid form It was confirmed that it was obtained as a single species that maintained the structure of the heteropolyacid. In this way, the modified free acid type heteropolyacid (Compound f) of Example 6 was obtained.
＜実施例２〜４、比較例１、２のシリカ薄膜の形成＞
化合物ａの代わりに化合物ｂ、ｃ、ｄ（実施例２〜４）、およびＨ3[ＰＷ12Ｏ40]（比較例１）、１Ｍ塩酸（比較例２）を用いて、表１の処方とした以外は実施例１と同様にして、母液Ｂ〜Ｄ、Ｇ、Ｈを作製した。なお、実施例１の母液Ａの処方も合わせて表１に示す。また、表１中のＨ+／テトラエトキシシラン（ｍｏｌ）の値については、すべて８．８×１０-2である。
<Formation of silica thin films of Examples 2 to 4 and Comparative Examples 1 and 2>
Using compounds b, c and d (Examples 2 to 4) instead of Compound a, and H 3 [PW 12 O 40 ] (Comparative Example 1) and 1M hydrochloric acid (Comparative Example 2), Except that, mother liquors B to D, G, and H were produced in the same manner as in Example 1. The formulation of mother liquor A of Example 1 is also shown in Table 1. Further, the values of H + / tetraethoxysilane (mol) in Table 1 are all 8.8 × 10 −2 .
次いで、母液Ａの代わりに母液Ｂ〜Ｄ、Ｇ、Ｈを用いて、表２の処方とした以外は実施例１と同様にして、希釈液Ｂ’〜Ｄ’、Ｇ’、Ｈ’を作製しシリカ薄膜を形成して、実施例２〜４、および比較例１、２の透明導電性シートを作製した。なお、実施例１の希釈液Ａ’の処方も合わせて表２に示す。 Next, using the mother liquors B to D, G and H instead of the mother liquor A, the dilute solutions B ′ to D ′, G ′ and H ′ were prepared in the same manner as in Example 1 except that the formulations shown in Table 2 were used. Then, a silica thin film was formed, and transparent conductive sheets of Examples 2 to 4 and Comparative Examples 1 and 2 were produced. The formulation of the diluent A ′ of Example 1 is also shown in Table 2.
［実施例７］
１．修飾物製造工程、およびシリカ薄膜の形成
Ｓｉ（ＯＥｔ）4 ０．４２ｇ（２ｍｍｏｌ）を純水／エタノール＝５０／５０ｍＬに分散させ、実施例１と同様の一欠損Ｄａｗｓｏｎ型タングストポリ酸塩Ｋ10［Ｐ2Ｗ17Ｏ61]・１９Ｈ2Ｏを５．０ｇ（１ｍｍｏｌ）加えた。１Ｍ塩酸を用いて溶液のｐＨを１．５に調整し、１時間攪拌した。この溶液に実施例１と同様のイオン交換樹脂５０ｇを加え、ゆっくりと攪拌した。イオン交換樹脂をろ別した後、Ｓｉ（ＯＥｔ）4 １４．２ｇを加えて２５℃で一晩ゾルゲル反応を進行させ、塗布液Ｉが得られた。
[Example 7]
1. Modified product production process and formation of silica thin film 0.42 g (2 mmol) of Si (OEt) 4 was dispersed in pure water / ethanol = 50/50 mL, and one-deficient Dawson-type Tungstopolyacid salt K 10 [Example 10 ] 5.0 g (1 mmol) of P 2 W 17 O 61 ] · 19H 2 O was added. The pH of the solution was adjusted to 1.5 using 1M hydrochloric acid and stirred for 1 hour. To this solution, 50 g of the same ion exchange resin as in Example 1 was added and stirred slowly. After the ion-exchange resin was filtered off, 14.2 g of Si (OEt) 4 was added and the sol-gel reaction was allowed to proceed overnight at 25 ° C. to obtain a coating liquid I.
塗布液Ｉを希釈液Ａ’の代わりに用いた以外は実施例１と同様にして、シリカ薄膜を形成して、実施例７の透明導電性シートを作製した。 A transparent conductive sheet of Example 7 was prepared by forming a silica thin film in the same manner as in Example 1 except that the coating liquid I was used instead of the diluent A ′.
［実施例８］
１．修飾物製造工程、およびシリカ薄膜の形成
Ａｌ（ＯＥｔ）3 ０．１６２ｇ（１ｍｍｏｌ）を純水４０ｍＬに分散させて、１Ｍ塩酸を用いて溶液のｐＨを１．５に調整した。得られた無色透明溶液に、実施例１と同様の一欠損Ｄａｗｓｏｎ型タングストポリ酸塩Ｋ10［Ｐ2Ｗ17Ｏ61］・１９Ｈ2Ｏを５．０ｇ（１ｍｍｏｌ）加えて１時間攪拌した。この溶液に実施例１と同様のイオン交換樹脂５０ｇを加え、ゆっくりと攪拌した。イオン交換樹脂をろ別した後、Ｓｉ（ＯＥｔ）4 １８．５ｇを加えて２５℃で一晩ゾルゲル反応を進行させ、塗布液Ｊが得られた。
[Example 8]
1. Modified product production process and formation of silica thin film 0.162 g (1 mmol) of Al (OEt) 3 was dispersed in 40 mL of pure water, and the pH of the solution was adjusted to 1.5 using 1 M hydrochloric acid. To the obtained colorless and transparent solution, 5.0 g (1 mmol) of one-deficient Dawson-type Tungstopolyacid salt K 10 [P 2 W 17 O 61 ] · 19H 2 O as in Example 1 was added and stirred for 1 hour. To this solution, 50 g of the same ion exchange resin as in Example 1 was added and stirred slowly. After the ion exchange resin was filtered off, 18.5 g of Si (OEt) 4 was added and the sol-gel reaction was allowed to proceed overnight at 25 ° C. to obtain coating solution J.
塗布液Ｊを希釈液Ａ’の代わりに用いた以外は実施例１と同様にして、シリカ薄膜を形成して、実施例８の透明導電性シートを作製した。 A transparent conductive sheet of Example 8 was produced by forming a silica thin film in the same manner as in Example 1 except that the coating liquid J was used instead of the diluent A ′.
＜表面抵抗率の算出＞
実施例２〜４、７、８、および比較例１、２で得られた透明導電性シートを用い、実施例１と同様にして表面抵抗を測定し表面抵抗率を算出した。測定は、透明導電性シートの作製直後（水に浸漬していないもの）について行なった。また、比較例１の透明導電性シートについては、水に１５時間浸漬後の測定も行なった。結果を表３に示す。また実施例１の結果についても合わせて表３に示す。なお、表３中の単位は、Ω／□である。
<Calculation of surface resistivity>
Using the transparent conductive sheets obtained in Examples 2 to 4, 7, 8, and Comparative Examples 1 and 2, the surface resistance was measured and the surface resistivity was calculated in the same manner as in Example 1. The measurement was performed immediately after the production of the transparent conductive sheet (not immersed in water). Moreover, about the transparent conductive sheet of the comparative example 1, the measurement after being immersed in water for 15 hours was also performed. The results are shown in Table 3. The results of Example 1 are also shown in Table 3. The unit in Table 3 is Ω / □.
＜ゾルゲル反応によって得られた粉体を使用した溶出試験＞
実施例１〜４、７、８、および比較例１、２で得られた加水分解溶液（母液Ａ〜Ｄ、Ｇ、Ｈ、および塗布液Ｉ、Ｊ）の溶媒を、７０℃、３時間加熱した後、１６０℃、５時間加熱して粉体（加水分解物）を取り出した。得られた粉体（加水分解物）が純水に溶出しないか確認する為、得られた粉体を２０ｍＬの純水に３日間浸して、上澄み溶液のｐＨをｐＨ試験紙を用いて調べた。結果を表４に示す。
<Elution test using powder obtained by sol-gel reaction>
The solvents of the hydrolysis solutions (mother liquors A to D, G, H, and coating solutions I and J) obtained in Examples 1 to 4, 7, 8 and Comparative Examples 1 and 2 were heated at 70 ° C. for 3 hours. After that, the powder (hydrolyzate) was taken out by heating at 160 ° C. for 5 hours. In order to confirm whether the obtained powder (hydrolyzate) does not elute in pure water, the obtained powder was immersed in 20 mL of pure water for 3 days, and the pH of the supernatant solution was examined using a pH test paper. . The results are shown in Table 4.
表３より、実施例１〜４、７、８のものは、水に浸漬前の状態で帯電防止性を有しており、実施例１のものは水に１５時間浸漬後、帯電防止性が殆ど低下しないものであった。また、表４より、実施例１〜４、７、８のものは、水に浸漬後、上澄み溶液のＰＨが中性付近を示している。これらの結果は、実施例のものは、修飾フリーアシッド型ヘテロポリ酸が担体に固定化されていることから、水に浸漬しても修飾フリーアシッド型ヘテロポリ酸がシリカ担体から殆どブリードアウトしていないことを示している。特に、実施例１のものは、修飾フリーアシッド型ヘテロポリ酸の加水分解物が導入された部分として（ＳｉＯＨ）2Ｏを用いていることから、テトラエトキシシランの加水分解物との間で縮合反応を起こす際に架橋構造をとることができ、シリカ薄膜の耐擦傷性や耐溶剤性に極めて優れるものであった。 From Table 3, Examples 1-4, 7 and 8 have antistatic properties before being immersed in water, and those of Example 1 have antistatic properties after being immersed in water for 15 hours. Almost no decrease. Moreover, from Table 4, the samples of Examples 1-4, 7, and 8 show that the pH of the supernatant solution is near neutral after being immersed in water. These results show that the modified free acid type heteropolyacid is hardly bleeded out from the silica support even when immersed in water because the modified free acid type heteropolyacid is immobilized on the support in the examples. It is shown that. In particular, since the thing of Example 1 uses (SiOH) 2 O as the part into which the hydrolyzate of modified free acid type heteropolyacid has been introduced, the condensation reaction with the hydrolyzate of tetraethoxysilane A cross-linked structure can be taken when causing the occurrence of scratches, and the silica thin film has extremely excellent scratch resistance and solvent resistance.
一方、比較例１のものは、表３より、水に浸漬前の状態で帯電防止性を有しているが、水に１５時間浸漬後は帯電防止性が著しく低下したものとなった。また表４より、水に浸漬後、ＰＨが酸性を示している。この結果は、比較例１のものは無置換のフリーアシッド型ヘテロポリ酸を用いているため、担体に固定化されていないことから、水に浸漬すると無置換のフリーアシッド型ヘテロポリ酸がシリカ担体からブリードアウトしてしまうことを示している。 On the other hand, although the thing of the comparative example 1 has antistatic property from the state before being immersed in water from Table 3, the antistatic property fell remarkably after being immersed in water for 15 hours. Moreover, from Table 4, PH shows acidity after being immersed in water. As a result, since the non-substituted free acid type heteropolyacid used in Comparative Example 1 is not immobilized on the support, the non-substituted free acid type heteropolyacid is removed from the silica support when immersed in water. It indicates that it will bleed out.
Ａ・・・ヘテロポリアニオン
Ｂ・・・担体
A ... heteropolyanion B ... carrier
Claims (3)
Ｈm[Ｘ（ＹＯＨ）aＯb]・ｎＨ2Ｏ ・・・（１）
[式中、Ｘは骨格構成原子の一部を欠損させたヘテロポリアニオンであり、ＹはＳｉ、Ｔｉ、Ａｌ、Ｚｒから選ばれる何れか１種の原子であり、ｍは１以上の整数であって一般式（１）中の[Ｘ（ＹＯＨ）aＯb]から決定される負電荷の絶対値であり、ｎは１以上の整数である。また、ａは１又は２であり、ｂはａが１のとき０、ａが２のとき１である。] The modified free acid type heteropolyacid according to claim 1, which is represented by the general formula (1).
H m [X (YOH) a O b ] · nH 2 O (1)
[Wherein, X is a heteropolyanion in which a part of the skeleton constituent atoms is missing, Y is any one atom selected from Si, Ti, Al and Zr, and m is an integer of 1 or more. The absolute value of the negative charge determined from [X (YOH) a O b ] in the general formula (1), and n is an integer of 1 or more. A is 1 or 2, b is 0 when a is 1, and 1 when a is 2. ]
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| JP2008031147A (en) * | 2006-06-30 | 2008-02-14 | Kimoto & Co Ltd | Modified free-acid type heteropolyacid, modified heteropolyacid salt and free-acid type heteropolyacid-based polymer |
| JP2009054580A (en) * | 2007-07-31 | 2009-03-12 | Kimoto & Co Ltd | Proton conductive electrolyte membrane for fuel cell |
| JP2011503300A (en) * | 2007-11-09 | 2011-01-27 | スリーエム イノベイティブ プロパティズ カンパニー | Polymer electrolyte containing heteropolyacid |
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| JPH06200185A (en) * | 1992-12-28 | 1994-07-19 | Sekisui Chem Co Ltd | Antistatic coating composition for plastic |
| JPH06320003A (en) * | 1993-05-10 | 1994-11-22 | Tokuyama Soda Co Ltd | Heteropolyacid carried catalyst |
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| JP2008031147A (en) * | 2006-06-30 | 2008-02-14 | Kimoto & Co Ltd | Modified free-acid type heteropolyacid, modified heteropolyacid salt and free-acid type heteropolyacid-based polymer |
| JP2009054580A (en) * | 2007-07-31 | 2009-03-12 | Kimoto & Co Ltd | Proton conductive electrolyte membrane for fuel cell |
| JP2011503300A (en) * | 2007-11-09 | 2011-01-27 | スリーエム イノベイティブ プロパティズ カンパニー | Polymer electrolyte containing heteropolyacid |
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