JP7250318B2 - Method and mixture for measuring hydrogen storage capacity of organic hydrides - Google Patents

Description

The present invention relates to a method and mixture for measuring the hydrogen storage capacity of organic hydrides.

A mixture of toluene (TOL) and methylcyclohexane (MCH) is known as a liquid organic hydride that is a hydrogen storage medium. In such a liquid organic hydride, the mixing ratio of TOL and MCH can be regarded as equivalent to the amount of hydrogen stored. Therefore, in order to know the amount of hydrogen stored in the liquid organic hydride, the mixing ratio of TOL and MCH is sometimes measured. be.

A gas chromatography method is known as a method for measuring the mixing ratio of TOL and MCH (Non-Patent Document 1).

On the other hand, it has been reported that when the polymerization reaction of a monosubstituted aromatic acetylene monomer with a rhodium complex catalyst is carried out in a poor solvent, the color of the resulting polymer changes depending on the polymerization solvent (Non-Patent Documents 2-4). .

Munjeong Jang et al, A High-Capacity, Reversible Liquid Organic Hydrogen Carrier: H2-Release Properties and an Application to a Fuel Cell, ACS Sustainable Chem. Eng. 2019, 7, 1185-1194 Ａｓａｈｉ Ｍｏｔｏｓｈｉｇｅ ｅｔ ａｌ，Ｉｒｒｅｖｅｒｓｉｂｌｅ Ｈｅｌｉｘ Ｒｅａｒｒａｎｇｅｍｅｎｔ ｆｒｏｍ Ｃｉｓ－Ｔｒａｎｓｏｉｄ ｔｏ Ｃｉｓ－Ｃｉｓｏｉｄ ｉｎ Ｐｏｌｙ（ｐ－ｎ－ｈｅｘｙｌｏｘｙｐｈｅｎｙｌａｃｅｔｙｌｅｎｅ）Ｉｎｄｕｃｅｄ ｂｙ Ｈｅａｔ－Ｔｒｅａｔｍｅｎｔ ｉｎ Ｓｏｌｉｄ Ｐｈａｓｅ，ＪＯＵＲＮＡＬ ＯＦ ＰＯＬＹＭＥＲ ＳＣＩＥＮＣＥ ＰＡＲＴ Ａ：ＰＯＬＹＭＥＲ ＣＨＥＭＩＳＴＲＹ ２０１２，５０，３００８－３０１５ Ｙａｓｕｔｅｒｕ Ｍａｗａｔａｒｉ ｅｔ ａｌ，Ｓｔｒｕｃｔｕｒａｌ ｄｅｔｅｒｍｉｎａｔｉｏｎ ｏｆ ｓｔｒｅｔｃｈｅｄ ｈｅｌｉｘ ａｎｄ ｃｏｎｔｒａｃｔｅｄ ｈｅｌｉｘ ｈａｖｉｎｇ ｙｅｌｌｏｗ ａｎｄ ｒｅｄ ｃｏｌｏｒｓ ｏｆ ｐｏｌｙ（２－ｅｔｈｙｎｙｌｎａｐｈｔｈａｌｅｎｅ）ｐｒｅｐａｒｅｄ ｗｉｔｈ ａ ［Ｒｈ（ｎｏｒｂｏｒｎａｄｉｅｎｅ）Ｃｌ］２－ｔｒｉｅｔｈｙｌａｍｉｎｅ ｃａｔａｌｙｓｔ，Ｐｏｌｙｍｅｒ ５５（２０１４）２３５６－２３６１ Ｙａｓｕｔｅｒｕ Ｍａｗａｔａｒｉ ｅｔ ａｌ，Ｍｅｔｈｏｘｙ－Ｇｒｏｕｐ Ｃｏｎｔｒｏｌ ｏｆ Ｈｅｌｉｃａｌ Ｐｉｔｃｈ ｉｎ Ｓｔｅｒｅｏｒｅｇｕｌａｒ Ｐｏｌｙ（２－ｅｔｈｙｎｙｌｍｅｔｈｏｘｙｎａｐｈｔｈａｌｅｎｅ）Ｐｒｅｐａｒｅｄ ｂｙ Ｒｈｏｄｉｕｍ Ｃｏｍｐｌｅｘ Ｃａｔａｌｙｓｔ，Ｐｏｌｙｍｅｒｓ ２０１９，１１，９４；ｄｏｉ：１０．３３９０／ｐｏｌｙｍ１１０１００９４

However, when measuring the mixing ratio of TOL and MCH in a liquid organic hydride by gas chromatography, the gas chromatography method requires a large-sized apparatus, and the apparatus start-up time and analysis time take at least one hour or more. In addition, since helium gas (strategic substance) is used as carrier gas and hydrogen gas is used for combustion in the detector, the measurement cost is extremely high.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method and a mixture for measuring the hydrogen storage amount that can easily and inexpensively measure the hydrogen storage amount of an organic hydride.

（式中、Ｒは、置換基を有していてもよいナフチル基、フルオレニル基、フェニル基、アントリル基、トリフェニレニル基、ビフェニル基、トリフェニル基、ピレニル基、ベンゾクリセニル基、フルオランテニル基、フェナントリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、インデニル基、アズレニル基、ビフェニレン基、ペリレニル基、ピセニル基、チエニル基及びフラニル基からなる群より少なくとも１つ選択される）で表される一置換アセチレンモノマーの重合反応により、一般式（ＩＩ）

（式中、ｎは、１０～１００，０００の整数であり、Ｒは前記一般式（Ｉ）におけるものと同じ基を表す）で表される一置換ポリアセチレンを得る工程と、
（Ｂ）前記工程（Ａ）で得られた前記一置換ポリアセチレンの色彩を観察する工程と、
（Ｃ）前記工程（Ｂ）で観察された前記色彩に基づき、前記有機ハイドライド中のメチルシクロヘキサン（ＭＣＨ）とトルエン（ＴＯＬ）との混合比を測定する工程と、
を含む、
ことを特徴とする。 In order to achieve the above object, the method for measuring the hydrogen storage capacity of an organic hydride according to the first aspect of the present invention comprises:
(A) in the organic hydride, general formula (I)

(In the formula, R is a naphthyl group, fluorenyl group, phenyl group, anthryl group, triphenylenyl group, biphenyl group, triphenyl group, pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, which may have a substituent. at least one selected from the group consisting of a group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenyl group, an azulenyl group, a biphenylene group, a perylenyl group, a picenyl group, a thienyl group and a furanyl group) By polymerization reaction of monosubstituted acetylene monomer, general formula (II)

(Wherein, n is an integer of 10 to 100,000, and R represents the same group as in the general formula (I));
(B) a step of observing the color of the monosubstituted polyacetylene obtained in the step (A);
(C) measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color observed in step (B);
including,
It is characterized by

For example, in the step (B), the color is observed based on the absorption band in the wavelength range of 350-750 nm.

For example, R is an optionally substituted naphthyl or fluorenyl group.

（式中、Ｒは、置換基を有していてもよいナフチル基、フルオレニル基、フェニル基、アントリル基、トリフェニレニル基、ビフェニル基、トリフェニル基、ピレニル基、ベンゾクリセニル基、フルオランテニル基、フェナントリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、インデニル基、アズレニル基、ビフェニレン基、ペリレニル基、ピセニル基、チエニル基及びフラニル基からなる群より少なくとも１つ選択される）で表される化合物と、有機ハイドライドとを含む。 The mixture for measuring hydrogen storage amount according to the second aspect of the present invention is
general formula (I)

(In the formula, R is a naphthyl group, fluorenyl group, phenyl group, anthryl group, triphenylenyl group, biphenyl group, triphenyl group, pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, which may have a substituent. at least one selected from the group consisting of a group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenyl group, an azulenyl group, a biphenylene group, a perylenyl group, a picenyl group, a thienyl group and a furanyl group) compounds and organic hydrides .

（式中、ｎは、１０～１００，０００の整数であり、Ｒは、置換基を有していてもよいナフチル基、フルオレニル基、フェニル基、アントリル基、トリフェニレニル基、ビフェニル基、トリフェニル基、ピレニル基、ベンゾクリセニル基、フルオランテニル基、フェナントリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、インデニル基、アズレニル基、ビフェニレン基、ペリレニル基、ピセニル基、チエニル基及びフラニル基からなる群より少なくとも１つ選択される）で表される一置換ポリアセチレンを添加する工程と、
（Ｂ）前記工程（Ａ）で添加された前記一置換ポリアセチレンの色彩を観察する工程と、
（Ｃ）前記工程（Ｂ）で観察された前記色彩に基づき、前記有機ハイドライド中のメチルシクロヘキサン（ＭＣＨ）とトルエン（ＴＯＬ）との混合比を測定する工程と、
を含む、
ことを特徴とする。 A method for measuring the hydrogen storage capacity of an organic hydride according to the third aspect of the present invention comprises:
(A) In the organic hydride, general formula (II)

(Wherein, n is an integer of 10 to 100,000, R is a naphthyl group optionally having a substituent, a fluorenyl group, a phenyl group, anthryl group, a triphenylenyl group, a biphenyl group, a triphenyl group , pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, indenyl group, azulenyl group, biphenylene group, perylenyl group, picenyl group, thienyl group and furanyl group a step of adding a monosubstituted polyacetylene represented by at least one selected from the group;
(B) observing the color of the monosubstituted polyacetylene added in step (A);
(C) measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color observed in step (B);
including,
It is characterized by

For example, in the step (B), the color is observed based on the absorption band in the wavelength range of 350-750 nm.

For example, R is an optionally substituted naphthyl or fluorenyl group.

（式中、ｎは、１０～１００，０００の整数であり、Ｒは、置換基を有していてもよいナフチル基、フルオレニル基、フェニル基、アントリル基、トリフェニレニル基、ビフェニル基、トリフェニル基、ピレニル基、ベンゾクリセニル基、フルオランテニル基、フェナントリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、インデニル基、アズレニル基、ビフェニレン基、ペリレニル基、ピセニル基、チエニル基及びフラニル基からなる群より少なくとも１つ選択される）で表される化合物と、有機ハイドライドとを含む。 The mixture for measuring hydrogen storage amount according to the fourth aspect of the present invention is
general formula (II)

(Wherein, n is an integer of 10 to 100,000, R is a naphthyl group optionally having a substituent, a fluorenyl group, a phenyl group, anthryl group, a triphenylenyl group, a biphenyl group, a triphenyl group , pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, indenyl group, azulenyl group, biphenylene group, perylenyl group, picenyl group, thienyl group and furanyl group at least one selected from the group) and an organic hydride.

ADVANTAGE OF THE INVENTION According to this invention, the method and the mixture for hydrogen storage amount measurement which can measure the hydrogen storage amount of an organic hydride simply and at low cost can be provided.

FIG. 2 is a photographic diagram showing the color change of monosubstituted polyacetylene precipitated in a TOL-MCH mixed solution, (a) being a photographic diagram of P2EN and (b) being a photographic diagram of P2EF. FIG. 2 is a diagram showing absorption spectra of P2EN precipitated by a polymerization reaction in a TOL-MCH mixture. FIG. 4 shows absorption spectra of P2EN immersed in a TOL-MCH mixture.

First, a method for measuring the hydrogen storage capacity of organic hydride according to the present embodiment will be described in detail.

（式中、Ｒは、置換基を有していてもよいナフチル基、フルオレニル基、フェニル基、アントリル基、トリフェニレニル基、ビフェニル基、トリフェニル基、ピレニル基、ベンゾクリセニル基、フルオランテニル基、フェナントリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、インデニル基、アズレニル基、ビフェニレン基、ペリレニル基、ピセニル基、チエニル基及びフラニル基からなる群より少なくとも１つ選択される）で表される一置換アセチレンモノマーの重合反応により、一般式（ＩＩ）

（式中、ｎは、１０～１００，０００の整数であり、Ｒは前記一般式（Ｉ）におけるものと同じ基を表す）で表される一置換ポリアセチレンを得る工程と、
（Ｂ）前記工程（Ａ）で得られた前記一置換ポリアセチレンの色彩を観察する工程と、
（Ｃ）前記工程（Ｂ）で観察された前記色彩に基づき、前記有機ハイドライド中のメチルシクロヘキサン（ＭＣＨ）とトルエン（ＴＯＬ）との混合比を測定する工程と、
を含む。 The method for measuring the hydrogen storage capacity of an organic hydride according to this embodiment comprises:
(A) in the organic hydride, general formula (I)

(In the formula, R is a naphthyl group, fluorenyl group, phenyl group, anthryl group, triphenylenyl group, biphenyl group, triphenyl group, pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, which may have a substituent. at least one selected from the group consisting of a group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenyl group, an azulenyl group, a biphenylene group, a perylenyl group, a picenyl group, a thienyl group and a furanyl group) By polymerization reaction of monosubstituted acetylene monomer, general formula (II)

(Wherein, n is an integer of 10 to 100,000, and R represents the same group as in the general formula (I));
(B) a step of observing the color of the monosubstituted polyacetylene obtained in the step (A);
(C) measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color observed in step (B);
including.

The organic hydride used in the method of the present embodiment contains toluene (TOL) and methylcyclohexane (MCH) as main components, and is preferably a liquid organic hydride. The hydrogen content in the organic hydride, which is a hydrogen storage medium, corresponds to the mixing ratio of MCH and TOL. According to the method of the present embodiment, as will be described later, by observing the color of the organic hydride, the mixing ratio of MCH and TOL in the organic hydride can be grasped, and the hydrogen storage amount of the organic hydride can be measured. be able to. Hydrogen absorption and desorption of organic hydride are shown below.

で表され、式中、Ｒは、置換基を有していてもよいナフチル基、置換基を有していてもよいフルオレニル基、置換基を有していてもよいフェニル基、置換基を有していてもよいアントリル基、置換基を有していてもよいトリフェニレニル基、置換基を有していてもよいビフェニル基、置換基を有していてもよいトリフェニル基、置換基を有していてもよいピレニル基、置換基を有していてもよいベンゾクリセニル基、置換基を有していてもよいフルオランテニル基、置換基を有していてもよいフェナントリル基、置換基を有していてもよいジベンゾフラニル基、置換基を有していてもよいジベンゾチオフェニル基、置換基を有していてもよいカルバゾリル基、置換基を有していてもよいインデニル基、置換基を有していてもよいアズレニル基、置換基を有していてもよいビフェニレン基、置換基を有していてもよいペリレニル基、置換基を有していてもよいピセニル基、置換基を有していてもよいチエニル基及び置換基を有していてもよいフラニル基からなる群より少なくとも１つ選択される。Ｒは、１種類であってもよく、２種類以上であってもよい。つまり、工程（Ａ）で用いられる一置換ポリアセチレンは、例えば、Ｒがナフチル基のみの１種類の一置換ポリアセチレンであってもよく、又はＲがナフチル基の一置換ポリアセチレンとＲがフルオレニル基の一置換ポリアセチレンとの混合物（異なる構造を有する一置換ポリアセチレンの２以上の混合物）であってもよい。 The monosubstituted acetylene monomer used in step (A) has the general formula (I)

In the formula, R is a naphthyl group optionally having substituents, a fluorenyl group optionally having substituents, a phenyl group optionally having substituents, a substituent optionally substituted anthryl group, optionally substituted triphenylenyl group, optionally substituted biphenyl group, optionally substituted triphenyl group, optionally substituted optionally substituted pyrenyl group, optionally substituted benzochrysenyl group, optionally substituted fluoranthenyl group, optionally substituted phenanthryl group, optionally substituted dibenzofuranyl group optionally having substituent(s), dibenzothiophenyl group optionally having substituent(s), carbazolyl group optionally having substituent(s), indenyl group optionally having substituent(s), substituent azulenyl group optionally having substituents, biphenylene group optionally having substituents, perylenyl group optionally having substituents, picenyl group optionally having substituents, having substituents is at least one selected from the group consisting of an optionally substituted thienyl group and an optionally substituted furanyl group; One type of R may be used, or two or more types may be used. That is, the monosubstituted polyacetylene used in step (A) may be, for example, one type of monosubstituted polyacetylene in which R is only a naphthyl group, or a monosubstituted polyacetylene in which R is a naphthyl group and R is a monosubstituted polyacetylene in which R is a fluorenyl group. It may be a mixture with substituted polyacetylene (a mixture of two or more monosubstituted polyacetylenes having different structures).

In the above general formula (I), the substituents include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, linear, branched or cyclic alkyl groups such as cyclooctyl; alkenyl groups such as vinyl, allyl, crotyl, prenyl, 7-octenyl and cyclohexenyl; ethynyl, propynyl and propargyl , alkynyl groups such as phenylethynyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, n-hexyl group, cyclohexyloxy group, n-octyloxy group, n-decyloxy group, alkoxy groups such as n-dodecyloxy; alkylthio groups such as methylthio, ethylthio, propylthio, butylthio, phenylthio, and naphthylthio; tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy trisubstituted silyloxy group; acetoxy group, propanoyloxy group, butanoyloxy group, pivaloyloxy group, acyloxy group such as benzoyloxy group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group; sulfoxide groups such as foxide group, ethylsulfoxide group and phenylsulfoxide group; Acid ester group; primary or secondary amino group such as dimethylamino group, diphenylamino group, methylphenylamino group, methylamino group, ethylamino group; acetyl group, benzoyl group, benzenesulfonyl group, tert-butoxycarbonyl group an amino group optionally substituted with an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, or the like, or an aryl group substituted with a hydroxyl group; a cyano group; a nitro group; and halogen atoms such as a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

In general formula (I) above, R is preferably an optionally substituted naphthyl group or an optionally substituted fluorenyl group. The substituent is the same as described above.

（式中、ｎは、１０～１００，０００の整数であり、Ｒは前記一般式（Ｉ）におけるものと同じ基を表す）で表される一置換ポリアセチレンを得る。ｎは数平均重合度を表し、１０～１００，０００、好ましくは、１００～１００，０００の整数である。該重合反応を以下に示す。 In the step (A), the polymerization reaction of the monosubstituted acetylene monomer represented by the above general formula (I) yields the general formula (II)

(In the formula, n is an integer of 10 to 100,000, and R represents the same group as in the general formula (I)) to obtain a monosubstituted polyacetylene. n represents the number average degree of polymerization and is an integer of 10 to 100,000, preferably 100 to 100,000. The polymerization reaction is shown below.

In the step (A), the monosubstituted acetylene monomer represented by the general formula (I) is added to the organic hydride and polymerized. In the organic hydride, monosubstituted polyacetylene represented by general formula (II) is produced (for example, solid-state monosubstituted polyacetylene precipitates in the organic hydride).

A catalyst may be used in the polymerization reaction of the monosubstituted acetylene monomer. Examples of the catalyst include rhodium complexes, palladium complexes, iridium complexes and platinum complexes.

Examples of rhodium complexes include chlorotris(triphenylphosphine)rhodium, acetylacetonatobis(ethylene)rhodium, acetylacetonatobis(cyclooctene)rhodium, acetylacetonato(1,5-cyclooctadiene)rhodium, (1, 5-cyclooctadiene)bis(triphenylphosphine)rhodium hexafluorophosphate, (norbornadiene)tris(triphenylphosphine)rhodiumhexafluorophosphate, bis(1,5-cyclooctadiene)rhodiumtrifluoromethanesulfonate, bis(norbornadiene) rhodium tetrafluoroborate, chlorobis(ethylene)rhodium dimer, chlorobis(cyclooctene)rhodium dimer, chloro(1,5-cyclooctadiene)rhodium dimer, chloro(norbornadiene)rhodium dimer, chloro(dicyclopentadienyl)rhodium dimer , chloro(tetrafluorobenzovalerene) rhodium dimer, and the like.

Palladium complexes include, for example, dichloro(1,5-cyclooctadiene)palladium.

Iridium complexes include acetylacetonato(1,5-cyclooctadiene)iridium, bis(1,5-cyclooctadiene)iridium tetrafluoroborate, chlorobis(cyclooctene)iridium dimer, chloro(1,5-cyclooctadiene) diene) and iridium dimer.

Examples of platinum complexes include dichloro(1,5-cyclooctadiene)platinum and dichloro(dicyclopentadienyl)platinum.

From the viewpoint of polymerization activity and industrial availability, for example, chloro(norbornadiene)rhodium dimer ([Rh(nbd)Cl] ₂ ) can be used as a catalyst for the polymerization reaction of monosubstituted acetylene monomers.

In order to enhance the activity of the polymerization reaction, triethylamine (NEt ₃ ), tributylamine, tri-n-octylamine, N,N,N',N'-tetramethyl-1,2-diaminoethane, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N-diethylethanolamine, triethanol Additional additives such as amines, N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, pyridine, picoline, lutidine, collidine, quinoline, etc. may be added.

The monosubstituted polyacetylene represented by the general formula (II) is preferably sparingly soluble in organic hydride from the viewpoint of observing the color of the solid-state monosubstituted polyacetylene in step (B) described later. Here, "poorly soluble" means that the solubility in organic hydride is 1.0% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less.

In step (B), the color of the monosubstituted polyacetylene may be observed visually or by spectrum measurement (for example, a diffuse reflectance spectrum is measured with an ultraviolet-visible spectrophotometer). By visually observing the color, as will be described later, the mixing ratio of MCH and TOL in the organic hydride can be easily and inexpensively grasped, and the hydrogen storage amount of the organic hydride can be easily and inexpensively determined. It can be visualized and measured.

Also, in step (B), the color of the monosubstituted polyacetylene may be observed, for example, based on the absorption band in the wavelength region of 350-750 nm. In this case, the observation of the color based on the absorption band in the wavelength region of 350 to 750 nm may be performed visually or by spectral measurement (for example, measuring the diffuse reflectance spectrum with an ultraviolet-visible spectrophotometer). . The wavelength range is 350-750 nm, preferably 400-650 nm.

Step (C) is a step of measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color of the monosubstituted polyacetylene in the organic hydride.

The color of the monosubstituted polyacetylene present in the organic hydride changes stepwise depending on the mixing ratio of MCH and TOL. For example, when the monosubstituted polyacetylene is poly 2-ethynylnaphthalene (P2EN) or poly 2-ethynylfluorene (P2EF) (in the general formula (I) above, R is a naphthyl group or a fluorenyl group), a mixture of MCH and TOL Depending on the ratio, the color of P2EN or P2EF changes stepwise from yellow to orange to red, with red becoming more pronounced as the TOL mixture ratio increases. The color of the monosubstituted polyacetylene present in the organic hydride may be a color other than the yellow, orange and red described above depending on the difference in R in the general formula (I).

Thus, the color of the monosubstituted polyacetylene present in the organic hydride changes stepwise depending on the mixing ratio of MCH and TOL. The mixing ratio of MCH and TOL in the hydride can be measured. For example, when the monosubstituted polyacetylene is P2EN or P2EF (in general formula (I) above, R is a naphthyl group or a fluorenyl group), when the monosubstituted polyacetylene present in the organic hydride exhibits a red color, MCH is abundant. It can be estimated that the hydrogen storage capacity of the organic hydride is large. It can be estimated that the hydrogen storage capacity of In addition, using TOL-MCH mixed liquids prepared at various mixing ratios of MCH and TOL, the mixing ratio of MCH and TOL and the color change of monosubstituted polyacetylene were previously matched "MCH-TOL A "mixing ratio color sample" is prepared in advance, and the color observed by performing the method of this embodiment on the organic hydride to be measured is compared with the "MCH-TOL mixing ratio color sample", and MCH and The mixing ratio with TOL can be measured.

As described above, the color of the monosubstituted polyacetylene can be visually observed in the step (B). In this case, the mixing ratio of MCH and TOL in the organic hydride is easily visualized and measured at low cost. be able to. Since the mixing ratio of TOL and MCH in the organic hydride can be considered equivalent to the hydrogen storage capacity, the hydrogen storage capacity in the organic hydride can be estimated by measuring the mixing ratio of TOL and MCH in the organic hydride in step (C). can be measured.

Further, as described above, in the step (B), the color of the monosubstituted polyacetylene may be observed, for example, based on the absorption band in the wavelength region of 350 to 750 nm, and the observation of the color based on the absorption band is It may be performed by visual observation or by spectral measurement. For example, in the case of spectral measurement, when the absorption band shifts to the short wavelength side in the wavelength region of 350 to 750 nm, it is determined that MCH is abundantly contained in the organic hydride, and the hydrogen storage amount of the organic hydride On the other hand, when the absorption band shifts to the long wavelength side, it is judged that TOL is abundantly contained in the organic hydride, and the hydrogen storage amount of the organic hydride is small. can be estimated.

Next, the compound for measuring the hydrogen storage amount of organic hydride according to this embodiment will be described.

で表される一置換アセチレンモノマーであり、式中、Ｒは、置換基を有していてもよいナフチル基、置換基を有していてもよいフルオレニル基、置換基を有していてもよいフェニル基、置換基を有していてもよいアントリル基、置換基を有していてもよいトリフェニレニル基、置換基を有していてもよいビフェニル基、置換基を有していてもよいトリフェニル基、置換基を有していてもよいピレニル基、置換基を有していてもよいベンゾクリセニル基、置換基を有していてもよいフルオランテニル基、置換基を有していてもよいフェナントリル基、置換基を有していてもよいジベンゾフラニル基、置換基を有していてもよいジベンゾチオフェニル基、置換基を有していてもよいカルバゾリル基、置換基を有していてもよいインデニル基、置換基を有していてもよいアズレニル基、置換基を有していてもよいビフェニレン基、置換基を有していてもよいペリレニル基、置換基を有していてもよいピセニル基、置換基を有していてもよいチエニル基及び置換基を有していてもよいフラニル基からなる群より少なくとも１つ選択される。Ｒは、前述同様、１種類であってもよく、２種類以上であってもよい。置換基の詳細については、前述同様である。 The compound for measuring the hydrogen storage amount of an organic hydride according to the present embodiment has the general formula (I)

is a monosubstituted acetylene monomer represented by the formula, wherein R is a naphthyl group which may have a substituent, a fluorenyl group which may have a substituent, a fluorenyl group which may have a substituent phenyl group, optionally substituted anthryl group, optionally substituted triphenylenyl group, optionally substituted biphenyl group, optionally substituted triphenyl group optionally substituted pyrenyl group optionally substituted benzochrysenyl group optionally substituted fluoranthenyl group optionally substituted phenanthryl optionally substituted dibenzofuranyl group, optionally substituted dibenzothiophenyl group, optionally substituted carbazolyl group, optionally substituted optionally substituted indenyl group, optionally substituted azulenyl group, optionally substituted biphenylene group, optionally substituted perylenyl group, optionally substituted picenyl group, a thienyl group optionally having substituent(s), and a furanyl group optionally having substituent(s). As described above, one type of R may be used, or two or more types may be used. The details of the substituent are the same as those described above.

The hydrogen storage amount measuring compound (monosubstituted acetylene monomer) is added to an organic hydride (same as described above) and polymerized. Then, the monosubstituted polyacetylene represented by the general formula (II) is produced in the organic hydride (for example, the monosubstituted polyacetylene in solid state is precipitated in the organic hydride). By observing the color of the monosubstituted polyacetylene produced in the organic hydride, the mixing ratio of MCH and TOL in the organic hydride can be measured, and thus the hydrogen storage capacity of the organic hydride can be measured. A catalyst may be used in the polymerization reaction of the monosubstituted acetylene monomer. In addition, an additive such as triethylamine (NEt ₃ ) may be further added as necessary in order to enhance the activity of the polymerization reaction. The details of each term are the same as described above.

A method for measuring the hydrogen storage capacity of an organic hydride according to another embodiment will now be described in detail.

（式中、ｎは、１０～１００，０００の整数であり、Ｒは、置換基を有していてもよいナフチル基、フルオレニル基、フェニル基、アントリル基、トリフェニレニル基、ビフェニル基、トリフェニル基、ピレニル基、ベンゾクリセニル基、フルオランテニル基、フェナントリル基、ジベンゾフラニル基、ジベンゾチオフェニル基、カルバゾリル基、インデニル基、アズレニル基、ビフェニレン基、ペリレニル基、ピセニル基、チエニル基及びフラニル基からなる群より少なくとも１つ選択される）で表される一置換ポリアセチレンを添加する工程と、
（Ｂ）前記工程（Ａ）で添加された前記一置換ポリアセチレンの色彩を観察する工程と、
（Ｃ）前記工程（Ｂ）で観察された前記色彩に基づき、前記有機ハイドライド中のメチルシクロヘキサン（ＭＣＨ）とトルエン（ＴＯＬ）との混合比を測定する工程と、
を含む。 A method for measuring the hydrogen storage capacity of an organic hydride according to this embodiment comprises:
(A) In the organic hydride (same as above), the general formula (II)

(Wherein, n is an integer of 10 to 100,000, R is a naphthyl group optionally having a substituent, a fluorenyl group, a phenyl group, anthryl group, a triphenylenyl group, a biphenyl group, a triphenyl group , pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, indenyl group, azulenyl group, biphenylene group, perylenyl group, picenyl group, thienyl group and furanyl group a step of adding a monosubstituted polyacetylene represented by at least one selected from the group;
(B) observing the color of the monosubstituted polyacetylene added in step (A);
(C) measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color observed in step (B);
including.

で表され、式中、ｎは、１０～１００，０００の整数であり、Ｒは、置換基を有していてもよいナフチル基、置換基を有していてもよいフルオレニル基、置換基を有していてもよいフェニル基、置換基を有していてもよいアントリル基、置換基を有していてもよいトリフェニレニル基、置換基を有していてもよいビフェニル基、置換基を有していてもよいトリフェニル基、置換基を有していてもよいピレニル基、置換基を有していてもよいベンゾクリセニル基、置換基を有していてもよいフルオランテニル基、置換基を有していてもよいフェナントリル基、置換基を有していてもよいジベンゾフラニル基、置換基を有していてもよいジベンゾチオフェニル基、置換基を有していてもよいカルバゾリル基、置換基を有していてもよいインデニル基、置換基を有していてもよいアズレニル基、置換基を有していてもよいビフェニレン基、置換基を有していてもよいペリレニル基、置換基を有していてもよいピセニル基、置換基を有していてもよいチエニル基及び置換基を有していてもよいフラニル基からなる群より少なくとも１つ選択される。Ｒは、前述同様、１種類であってもよく、２種類以上であってもよい。ｎ及び置換基の詳細については、前述同様である。 The monosubstituted polyacetylene added in step (A) has the general formula (II)

In the formula, n is an integer of 10 to 100,000, R is a naphthyl group which may have a substituent, a fluorenyl group which may have a substituent, a substituent optionally substituted phenyl group, optionally substituted anthryl group, optionally substituted triphenylenyl group, optionally substituted biphenyl group, optionally substituted optionally substituted triphenyl group, optionally substituted pyrenyl group, optionally substituted benzochrysenyl group, optionally substituted fluoranthenyl group, optionally substituted optionally substituted phenanthryl group, optionally substituted dibenzofuranyl group, optionally substituted dibenzothiophenyl group, optionally substituted carbazolyl group, substituent indenyl group optionally having a substituent, azulenyl group optionally having a substituent, biphenylene group optionally having a substituent, perylenyl group optionally having a substituent, having a substituent is at least one selected from the group consisting of an optionally substituted picenyl group, an optionally substituted thienyl group and an optionally substituted furanyl group; As described above, one type of R may be used, or two or more types may be used. The details of n and substituents are the same as described above.

The monosubstituted polyacetylene represented by the general formula (II) is preferably sparingly soluble in organic hydride from the viewpoint of observing the color of the solid-state monosubstituted polyacetylene in step (B) described later. "Poorly soluble" is the same as described above.

In the step (B), the color of the monosubstituted polyacetylene may be observed visually as described above, or by spectral measurement (for example, the diffuse reflectance spectrum is measured with an ultraviolet-visible spectrophotometer). .

Also, in step (B), the color of the monosubstituted polyacetylene may be observed, for example, based on the absorption band in the wavelength region of 350-750 nm. In this case, the observation based on the absorption band in the wavelength region of 350 to 750 nm may be performed visually or by spectral measurement (for example, the diffuse reflectance spectrum is measured with an ultraviolet-visible spectrophotometer). The wavelength range is 350-750 nm, preferably 400-650 nm.

Step (C) is a step of measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color of the monosubstituted polyacetylene in the organic hydride.

The color of the monosubstituted polyacetylene present in the organic hydride changes stepwise depending on the mixing ratio of MCH and TOL. The change in color of monosubstituted polyacetylene is the same as described above.

Since the color of the monosubstituted polyacetylene present in the organic hydride changes stepwise depending on the mixing ratio of MCH and TOL, in the step (C), based on the color of the monosubstituted polyacetylene, MCH in the organic hydride and TOL can be measured. For example, when the monosubstituted polyacetylene is P2EN or P2EF (in general formula (I) above, R is a naphthyl group or a fluorenyl group), when the monosubstituted polyacetylene present in the organic hydride exhibits a red color, MCH is abundant. It can be estimated that the hydrogen storage capacity of the organic hydride is large. It can be estimated that the hydrogen storage capacity of In addition, using TOL-MCH mixed solutions prepared at various mixing ratios of MCH and TOL, the mixing ratio of MCH and TOL and the color change of monosubstituted polyacetylene were matched in advance with "MCH-TOL A "mixing ratio color sample" is prepared in advance, and the color observed by performing the method of the present embodiment on the organic hydride to be measured is compared with the "MCH-TOL mixing ratio color sample", and MCH and The mixing ratio with TOL can be measured.

As described above, the color of the monosubstituted polyacetylene can be visually observed in the step (B). In this case, the mixing ratio of MCH and TOL in the organic hydride is easily visualized and measured at low cost. be able to. Since the mixing ratio of TOL and MCH in the organic hydride can be considered equivalent to the hydrogen storage capacity, the hydrogen storage capacity in the organic hydride can be estimated by measuring the mixing ratio of TOL and MCH in the organic hydride in step (C). can be measured.

In addition, as described above, in the step (B), the color of the monosubstituted polyacetylene may be observed, for example, based on the absorption band in the wavelength range of 350 to 750 nm, and the observation based on the absorption band is performed by visual observation. may be performed, and may be performed by spectral measurement. For example, in the case of spectral measurement, when the absorption band shifts to the short wavelength side in the wavelength region of 350 to 750 nm, it is determined that MCH is abundantly contained in the organic hydride, and the hydrogen storage amount of the organic hydride On the other hand, when the absorption band shifts to the long wavelength side, it is judged that TOL is abundantly contained in the organic hydride, and the hydrogen storage amount of the organic hydride is small. can be estimated.

Next, a compound for measuring the hydrogen storage amount of an organic hydride according to another embodiment will be described.

で表される一置換ポリアセチレンであり、式中、ｎは、１０～１００，０００の整数であり、Ｒは、置換基を有していてもよいナフチル基、置換基を有していてもよいフルオレニル基、置換基を有していてもよいフェニル基、置換基を有していてもよいアントリル基、置換基を有していてもよいトリフェニレニル基、置換基を有していてもよいビフェニル基、置換基を有していてもよいトリフェニル基、置換基を有していてもよいピレニル基、置換基を有していてもよいベンゾクリセニル基、置換基を有していてもよいフルオランテニル基、置換基を有していてもよいフェナントリル基、置換基を有していてもよいジベンゾフラニル基、置換基を有していてもよいジベンゾチオフェニル基、置換基を有していてもよいカルバゾリル基、置換基を有していてもよいインデニル基、置換基を有していてもよいアズレニル基、置換基を有していてもよいビフェニレン基、置換基を有していてもよいペリレニル基、置換基を有していてもよいピセニル基、置換基を有していてもよいチエニル基及び置換基を有していてもよいフラニル基からなる群より少なくとも１つ選択される。Ｒは、前述同様、１種類であってもよく、２種類以上であってもよい。ｎ及び置換基の詳細については、前述同様である。 The organic hydride (same as described above) hydrogen storage amount measuring compound according to the present embodiment has the general formula (II)

In the formula, n is an integer of 10 to 100,000, R is a naphthyl group optionally having a substituent, optionally having a substituent fluorenyl group, optionally substituted phenyl group, optionally substituted anthryl group, optionally substituted triphenylenyl group, optionally substituted biphenyl group , optionally substituted triphenyl group, optionally substituted pyrenyl group, optionally substituted benzochrysenyl group, optionally substituted fluoranthenyl optionally substituted phenanthryl group optionally substituted dibenzofuranyl group optionally substituted dibenzothiophenyl group optionally substituted optionally substituted carbazolyl group, optionally substituted indenyl group, optionally substituted azulenyl group, optionally substituted biphenylene group, optionally substituted perylenyl group optionally substituted picenyl group, optionally substituted thienyl group and optionally substituted furanyl group. As described above, one type of R may be used, or two or more types may be used. The details of n and substituents are the same as described above.

When the hydrogen storage amount measuring compound (monosubstituted polyacetylene) is added to the organic hydride, the color changes depending on the mixing ratio of TOL and MCH in the organic hydride. , the mixing ratio of MCH and TOL in the organic hydride is measured, and thus the hydrogen storage capacity of the organic hydride can be measured. The details of each term are the same as described above.

As described above, it is possible to provide a simple and low-cost method for measuring the amount of hydrogen stored in an organic hydride by observing the color of the monosubstituted polyacetylene. In particular, by visually observing the color of monosubstituted polyacetylene, it is possible to quickly and easily determine the amount of hydrogen stored in organic hydride even at sites where it is impossible to install a large-scale apparatus such as that used in gas chromatography. It is expected that it can be visualized and measured.

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
Monosubstituted polyacetylene was synthesized in a TOL-MCH mixed solution (liquid organic hydride alternative solution) in which toluene (TOL) and methylcyclohexane (MCH) were mixed in various proportions, and the color of the monosubstituted polyacetylene depending on the TOL-MCH mixing ratio. Verified the changes.

(Polymerization reaction)
A TOL-MCH mixed solution (liquid organic hydride alternative) was prepared by mixing methylcyclohexane (MCH) (Wako Pure Chemical Industries, Ltd.) and toluene (TOL) (Junsei Chemical Co., Ltd.) at the following mixing ratio.
MCH:TOL=100:0
MCH:TOL=75:25
MCH:TOL=50:50
MCH:TOL=25:75
MCH:TOL=0:100

The TOL-MCH mixed solution was divided into two parts, and a monosubstituted acetylene monomer was added to one part to make "A solution", and a rhodium complex catalyst ([Rh(nbd)Cl] ₂ ) (2,5-Norbornadiene Rhodium (I)) was added to the other part. Chloride Dimer, Wako Pure Chemical Industries, Ltd.) and triethylamine (NEt ₃ ) (triethylamine, Kanto Chemical Co., Ltd.) were added to prepare "B solution". Two types of 2-ethynylnaphthalene (R=2EN) and 2-ethynylfluorene (R=2EF) shown below were used as monosubstituted acetylene monomers. 2-ethynylnaphthalene was synthesized by the method described in Yasuteru Mawatari et al, Polymer 55 (2014) 2356-2361. 2-ethynylfluorene was synthesized by the method described in SYNTHETIC COMMUNICATIONS, 28(14), 2571-2576 (1998).

When 2-ethynylnaphthalene (2EN) is used, the TOL-MCH mixture is divided into two 9.9 mL portions, and 300 mg of 2EN is added to one of the two, stirred and dissolved to form liquid A, and 4.5 mg of the rhodium complex catalyst and 4.5 mg of rhodium complex catalyst are added to the other. 136 μL of triethylamine was added, stirred and dissolved to obtain liquid B. Then, B liquid was added to A liquid.

When 2-ethynylfluorene (2EF) is used, the TOL-MCH mixture is divided into two parts of 7.9 mL each, and 300 mg of 2EF is added to one of them, stirred and dissolved to form liquid A, and 3.6 mg of a rhodium complex catalyst and 109 μL of triethylamine was added, stirred and dissolved to obtain a liquid B. Then, B liquid was added to A liquid.

At the same time that the B solution was added to the A solution, the mixed solution was vigorously shaken at room temperature for 15 seconds. The produced precipitates of monosubstituted polyacetylene (poly 2-ethynylnaphthalene (P2EN) and poly 2-ethynylfluorene (P2EF)) were filtered by suction, washed with the TOL-MCH mixture used in the reaction, and then decompressed at 40°C. Dried. The polymerization reaction is shown below.

(Color evaluation of generated polymer)
The generated precipitate (monosubstituted polyacetylene) was visually observed (Fig. 1). Both of the precipitates (P2EN and P2EF) were insoluble in the TOL-MCH mixture. Both P2EN (Fig. 1(a)) and P2EF (Fig. 1(b)) showed a stepwise change from yellow to red with increasing TOL content in the TOL-MCH mixture, MCH:TOL= At 0:100, red was most emphasized.

(Spectral evaluation of generated polymer)
Absorption spectra were measured to examine the color change in more detail. The diffuse reflectance spectrum of the formed precipitate (P2EN) was measured with a UV-visible spectrophotometer (Fig. 2). More specifically, 10 mg of the produced precipitate (P2EN) was mixed and diluted with 200 mg of alumina (FUJIFILM Wako Pure Chemical Industries, Ltd., α-alumina, 0.5 μm), and an integrating sphere unit ISN-723 was added to JASCO V-670. Diffuse reflectance spectra were measured after wearing. In addition, on the vertical axis of FIG. 2, based on a general method in this technical field, Kubelka-Munk transformation (transformation for improving quantitativeness when measuring diffuse reflectance) is performed, and the area value of each spectrum is transformed to the same value. We used an arbitrary unit normalized by As a result, it was found that this color change was caused by a change in the intensity ratio of the absorption bands at 450 nm and 550 nm. As the TOL content in the TOL-MCH mixture increased, the absorption band shifted to longer wavelengths.

This example revealed that the TOL-MCH mixing ratio in the liquid organic hydride can be grasped by observing the color change of the monosubstituted polyacetylene produced by the polymerization reaction from the monosubstituted acetylene monomer in the liquid organic hydride. . From the above, it was shown that the hydrogen storage amount in the liquid organic hydride can be measured by using the method of this example. In particular, by visually observing the color change of the monosubstituted polyacetylene, it is expected that the amount of hydrogen stored in the liquid organic hydride can be visualized and measured within several minutes.

(Example 2)
A monosubstituted polyacetylene was immersed in a TOL-MCH mixed solution (liquid organic hydride alternative solution) in which TOL and MCH were mixed at various ratios, and the color change of the monosubstituted polyacetylene depending on the TOL-MCH mixing ratio was verified.

As the TOL-MCH mixed solution (liquid organic hydride substitute), the following mixed ratio was used. The method for preparing the TOL-MCH mixture is the same as in Example 1.
MCH:TOL=100:0
MCH:TOL=50:50
MCH:TOL=0:100

After immersing a small piece (size: 1-5 mm square, weight: 5-50 mg) of P2EN (monosubstituted polyacetylene) (synthesized by the method described in Polymer 55 (2014) 2356-2361) in the TOL-MCH mixed solution , held for 1 minute, and collected by filtration.

The diffuse reflectance spectrum of the collected P2EN was measured with an ultraviolet-visible spectrophotometer in the same manner as in Example 1 (FIG. 3). Note that the vertical axis in FIG. 3 uses an arbitrary unit as in FIG. As the TOL content in the TOL-MCH mixture increased, the absorption band shifted to longer wavelengths.

This example revealed that the TOL-MCH mixture ratio in the liquid organic hydride can be grasped by immersing the monosubstituted polyacetylene in the liquid organic hydride and observing the color change of the monosubstituted polyacetylene. From the above, it was shown that the hydrogen storage amount in the liquid organic hydride can be measured by using the method of this example.

Claims (8)

(A) in the organic hydride, general formula (I)

(In the formula, R is a naphthyl group, fluorenyl group, phenyl group, anthryl group, triphenylenyl group, biphenyl group, triphenyl group, pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, which may have a substituent. at least one selected from the group consisting of a group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenyl group, an azulenyl group, a biphenylene group, a perylenyl group, a picenyl group, a thienyl group and a furanyl group) By polymerization reaction of monosubstituted acetylene monomer, general formula (II)

(Wherein, n is an integer of 10 to 100,000, and R represents the same group as in the general formula (I));
(B) a step of observing the color of the monosubstituted polyacetylene obtained in the step (A);
(C) measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color observed in step (B);
including,
A method for measuring the hydrogen storage capacity of an organic hydride, characterized by: In the step (B), the color is observed based on the absorption band in the wavelength range of 350 to 750 nm.
2. The method of claim 1, wherein: R is an optionally substituted naphthyl group or fluorenyl group,
3. A method according to claim 1 or 2, characterized in that: general formula (I)

(In the formula, R is a naphthyl group, fluorenyl group, phenyl group, anthryl group, triphenylenyl group, biphenyl group, triphenyl group, pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, which may have a substituent. at least one selected from the group consisting of a group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, an indenyl group, an azulenyl group, a biphenylene group, a perylenyl group, a picenyl group, a thienyl group and a furanyl group) A mixture for hydrogen storage amount measurement , comprising a compound and an organic hydride. (A) In the organic hydride, general formula (II)

(Wherein, n is an integer of 10 to 100,000, R is a naphthyl group optionally having a substituent, a fluorenyl group, a phenyl group, anthryl group, a triphenylenyl group, a biphenyl group, a triphenyl group , pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, indenyl group, azulenyl group, biphenylene group, perylenyl group, picenyl group, thienyl group and furanyl group a step of adding a monosubstituted polyacetylene represented by at least one selected from the group;
(B) observing the color of the monosubstituted polyacetylene added in step (A);
(C) measuring the mixing ratio of methylcyclohexane (MCH) and toluene (TOL) in the organic hydride based on the color observed in step (B);
including,
A method for measuring the hydrogen storage capacity of an organic hydride, characterized by: In the step (B), the color is observed based on the absorption band in the wavelength range of 350 to 750 nm.
6. The method of claim 5, wherein: R is an optionally substituted naphthyl group or fluorenyl group,
7. A method according to claim 5 or 6, characterized in that: general formula (II)

(Wherein, n is an integer of 10 to 100,000, R is a naphthyl group optionally having a substituent, a fluorenyl group, a phenyl group, anthryl group, a triphenylenyl group, a biphenyl group, a triphenyl group , pyrenyl group, benzochrysenyl group, fluoranthenyl group, phenanthryl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, indenyl group, azulenyl group, biphenylene group, perylenyl group, picenyl group, thienyl group and furanyl group at least one selected from the group) and an organic hydride .

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