JP2018065702A - Polymer of chloride having silafluorene skeleton and method for producing the same - Google Patents
Polymer of chloride having silafluorene skeleton and method for producing the same Download PDFInfo
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本発明は、シラフラーラン骨格を有する塩素化物の重合体およびその製造方法に関する。 The present invention relates to a polymer of a chlorinated product having a shirarahralane skeleton and a method for producing the same.
理論計算上、［２０］シラフラーラン（Ｓｉ２０Ｈ２０）はＬｉやＮａのようなアルカリ金属を内包したり（非特許文献１）、バンドギャップが３．６４ｅＶ（非特許文献２）と言われており、リチウムイオン電池の負極材や半導体特性、光学特性が期待される。また［２０］シラフラーラン骨格を有する塩素化物の重合体になることで［２０］シラフラーランの有する物性の増幅、置換基導入による化合物の安定化が期待される。 According to theoretical calculations, [20] shirarahraran (Si 20 H 20 ) contains an alkali metal such as Li or Na (Non-patent Document 1), and the band gap is said to be 3.64 eV (Non-patent Document 2). Therefore, negative electrode materials, semiconductor characteristics, and optical characteristics of lithium ion batteries are expected. [20] By becoming a polymer of a chlorinated product having a silaflalan skeleton, the amplification of physical properties possessed by [20] silaflarane and the stabilization of the compound by introduction of substituents are expected.
理論計算上、存在するといわれていた［２０］シラフラーラン（Ｓｉ２０Ｈ２０）であるが、その［２０］シラフラーランの塩素化物［ｎ−Ｂｕ４Ｎ］［Ｓｉ３２Ｃｌ４５］の合成法が２０１５年に開発された（特許文献１、非特許文献３）。 Although it is [20] shiraralane (Si 20 H 20 ), which was said to exist in theoretical calculation, the synthesis method of the chlorinated product [n-Bu 4 N] [Si 32 Cl 45 ] of the [20] shirara lane was 2015. (Patent Document 1, Non-Patent Document 3).
ケイ素―ケイ素結合形成には大きく分けて２つある。第一にクロロシラン類とアルカリ金属を共存させることでＷｕｒｔｚ型反応による方法と第二にシラン類と触媒による脱水素化反応による方法がある。 There are two main types of silicon-silicon bond formation. First, there is a method based on a Wurtz type reaction by coexisting chlorosilanes and an alkali metal, and secondly, a method based on a dehydrogenation reaction using silanes and a catalyst.
理論計算上、［２０］シラフラーラン（Ｓｉ２０Ｈ２０）はＬｉやＮａのアルカリ金属を内包したり、バンドギャップが３．６４ｅＶという物性を有する。また［２０］シラフラーラン骨格を複数個有する重合体はこれらの物性をさらに増幅させたユニークな機能性材料になる可能性がある。［２０］シラフラーラン骨格を複数個含有する塩素化物の重合体の報告例はなく、その報告例のない［２０］シラフラーラン骨格を複数有する塩素化物の重合体及びその製造方法を見出した。 In theoretical calculation, [20] shirarahralane (Si 20 H 20 ) has a physical property of including an alkali metal of Li or Na or having a band gap of 3.64 eV. [20] A polymer having a plurality of shirarahralane skeletons may be a unique functional material obtained by further amplifying these physical properties. [20] There have been no reports of chlorinated polymers containing a plurality of shirakura lane skeletons, and [20] chlorinated polymers having a plurality of shirara uranium skeletons and a method for producing the same have been found.
本発明者らは、上記目的を達成すべく検討を重ねた結果、有機溶媒中、［２０］シラフラーランの塩素化物と反応剤を混合させることで、［２０］シラフラーラン骨格を複数個有する塩素化物の重合体の製造手法を見出し、本発明を完成させた。 As a result of repeated studies to achieve the above-mentioned object, the present inventors have mixed a chlorinated product of [20] shirafarran with a reactant in an organic solvent, thereby producing a chlorinated product having a plurality of [20] silaclarane skeletons. The production method of the polymer was found and the present invention was completed.
すなわち、本発明は、以下の構成からなる。
〔１〕 下記一般式（１）で表される［２０］シラフラーラン骨格を有するユニットを少なくとも２つは有することを特徴とする［２０］シラフラーラン骨格を有する塩素化物の重合体。
［Ｓｉ２０（ＳｉＣｌ２）ｅ（ＳｉＣｌａＭｂ）ｆ（ＳｉＣｌｃＭｄ）ｇＣｌｍＭｎ］ （１）
（前記式（１）中、Ｍはアルカリ金属、１２≧ｅ≧０、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、１１≧ｆ≧０、ｃ＋ｄ＝２、ｃ＝０〜２、ｄ＝０〜２、１２≧ｇ≧０、ｅ＋ｆ＋ｇ＝１２、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４の整数を示す。）
〔２〕 ［２０］シラフラーラン骨格を有する塩素化物を原料にし、有機溶媒中、−８０℃から２５０℃の範囲で反応剤と混合させることにより、前記一般式（１）で表される［２０］シラフラーラン骨格を少なくとも２以上有する重合体を製造することを特徴とするシラフラーラン骨格を有する塩素化物の重合体の製造方法。
〔２〕 前記反応剤が、アルカリ金属からなる群より少なくとも１種の金属を含む化合物である前記〔２〕に記載のシラフラーラン骨格を有する塩素化物の重合体の製造方法。
〔４〕 前記原料の［２０］シラフラーラン骨格を有する塩素化物の塩素のモル比に対して、反応剤は０．０１ｍｏｌ％〜５００ｍｏｌ％である前記〔２〕又は前記〔３〕に記載のシラフラーラン骨格を有する塩素化物の重合体の製造方法。
〔５〕 前記有機溶媒はテトラヒドロフラン（ＴＨＦ）、１、４−ジオキサン、ジエチルエーテル、トルエン、メチルシクロヘキサン、クラウンエーテル、キシレン、トリメチルベンゼン、１、２、３、４−テトラヒドロナフタレン、ペンタン、ノルマルヘキサン、シクロヘキサン、１、２−ジメトキシエタンよりすくなくとも１種を含む有機溶媒である前記〔２〕〜〔４〕のいずれかに記載のシラフラーラン骨格を有する塩素化物の重合体の製造方法。
That is, this invention consists of the following structures.
[1] A polymer of a chlorinated product having a [20] silaflalan skeleton, characterized in that it has at least two units having the [20] silaflalan skeleton represented by the following general formula (1).
[Si 20 (SiCl 2) e (SiCl a M b) f (SiCl c M d) g Cl m M n] (1)
(In the formula (1), M is an alkali metal, 12 ≧ e ≧ 0, a + b = 3, a = 0-3, b = 0-3, 11 ≧ f ≧ 0, c + d = 2, c = 0-2. D = 0-2, 12 ≧ g ≧ 0, e + f + g = 12, m + n = 45, m = 1-45, n = 0-44.
[2] [20] Represented by the general formula (1) by using, as a raw material, a chlorinated product having a shirarahralane skeleton, and mixing with a reactant in an organic solvent in the range of −80 ° C. to 250 ° C. [20] A method for producing a polymer of a chlorinated product having a silaflalan skeleton, comprising producing a polymer having at least two silaflalan skeletons.
[2] The method for producing a polymer of a chlorinated product having a shirakuraran skeleton according to [2], wherein the reactant is a compound containing at least one metal from the group consisting of alkali metals.
[4] The silaflarane skeleton according to the above [2] or [3], wherein the reactant is 0.01 mol% to 500 mol% with respect to the molar ratio of chlorine in the chlorinated product having the [20] shirafarran skeleton as the raw material. A method for producing a chlorinated polymer having
[5] The organic solvent is tetrahydrofuran (THF), 1,4-dioxane, diethyl ether, toluene, methylcyclohexane, crown ether, xylene, trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, pentane, normal hexane, The method for producing a polymer of a chlorinated product having a silaclaran skeleton according to any one of the above [2] to [4], which is an organic solvent containing at least one kind of cyclohexane and 1,2-dimethoxyethane.
本発明によれば、［２０］シラフラーラン骨格を複数個有する塩素化物の重合体を合成する方法を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the method of synthesize | combining the polymer of the chlorination thing which has two or more [20] shirarahralane skeletons.
本発明の［２０］シラフラーラン骨格を有する塩素化物の重合体は、下記一般式（１）で表される［２０］シラフラーラン骨格を有するユニットを少なくとも２つは有する。
［Ｓｉ２０（ＳｉＣｌ２）ｅ（ＳｉＣｌａＭｂ）ｆ（ＳｉＣｌｃＭｄ）ｇＣｌｍＭｎ］ （１）
（前記式（１）中、Ｍはアルカリ金属、１２≧ｅ≧０、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、１１≧ｆ≧０、ｃ＋ｄ＝２、ｃ＝０〜２、ｄ＝０〜２、１２≧ｇ≧０、ｅ＋ｆ＋ｇ＝１２、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４の整数を示す。）
The polymer of a chlorinated product having a [20] silaclaran skeleton of the present invention has at least two units having a [20] silaclaran skeleton represented by the following general formula (1).
[Si 20 (SiCl 2) e (SiCl a M b) f (SiCl c M d) g Cl m M n] (1)
(In the formula (1), M is an alkali metal, 12 ≧ e ≧ 0, a + b = 3, a = 0-3, b = 0-3, 11 ≧ f ≧ 0, c + d = 2, c = 0-2. D = 0-2, 12 ≧ g ≧ 0, e + f + g = 12, m + n = 45, m = 1-45, n = 0-44.
前記式（１）中で（ＳｉＣｌ２）ｅ、（ＳｉＣｌｃＭｄ）ｇの部分は、（Ｓｉ−Ｓｉ）の結合を形成している部分である。 In the above formula (1), the portions (SiCl 2 ) e and (SiCl c M d ) g are portions that form (Si—Si) bonds.
本発明の［２０］シラフラーラン骨格を有する塩素化物のユニットが（Ｓｉ−Ｓｉ）の結合で２つの前記ユニットが結合したものが、重合体の最小のもので、２量体であり、
［Ｓｉ２０（ＳｉＣｌ２）（ＳｉＣｌａＭｂ）１１ＣｌｍＭｎ］２
（式中、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４）
もしくは、
［Ｓｉ２０（ＳｉＣｌａＭｂ）１１（ＳｉＣｌｃＭｄ）ＣｌｍＭｎ］２
（式中、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、ｃ＋ｄ＝２、ｃ＝０〜２、ｄ＝０〜２、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４）
の化学式で表される。
The [20] chlorinated unit having a shirarahralane skeleton of the present invention, in which two units are bonded by a bond of (Si-Si), is the smallest polymer and is a dimer,
[Si 20 (SiCl 2) ( SiCl a M b) 11 Cl m M n] 2
(Where, a + b = 3, a = 0-3, b = 0-3, m + n = 45, m = 1-45, n = 0-44)
Or
[Si 20 (SiCl a M b ) 11 (SiCl c M d) Cl m M n] 2
(Where, a + b = 3, a = 0-3, b = 0-3, c + d = 2, c = 0-2, d = 0-2, m + n = 45, m = 1-45, n = 0 44)
It is represented by the chemical formula
本発明の［２０］シラフラーラン骨格を有する塩素化物のユニットが（Ｓｉ−Ｓｉ）の結合で３つの前記ユニットがリニアに結合した３量体は、
［Ｓｉ２０（ＳｉＣｌ２）（ＳｉＣｌａＭｂ）１１ＣｌｍＭｎ］２［Ｓｉ２０（ＳｉＣｌ２）２（ＳｉＣｌａＭｂ）１０ＣｌｍＭｎ］
（式中、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４）、
もしくは
［Ｓｉ２０（ＳｉＣｌａＭｂ）１１（ＳｉＣｌｃＭｄ）ＣｌｍＭｎ］２［Ｓｉ２０（ＳｉＣｌａＭｂ）１０（ＳｉＣｌｃＭｄ）２ＣｌｍＭｎ］
（式中、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、ｃ＋ｄ＝２、ｃ＝０〜２、ｄ＝０〜２、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４）
の化学式で表される。前記式（１）中で（ＳｉＣｌａＭｂ）ｆの部分は重合反応に関与していない、重合体の末端部位であることを示す。
The [20] chlorinated unit having a shirarahralane skeleton of the present invention is a trimer in which three units are linearly bonded with a bond of (Si-Si),
[Si 20 (SiCl 2) ( SiCl a M b) 11 Cl m M n] 2 [Si 20 (SiCl 2) 2 (SiCl a M b) 10 Cl m M n]
(Where, a + b = 3, a = 0-3, b = 0-3, m + n = 45, m = 1-45, n = 0-44),
Or [Si 20 (SiCl a M b ) 11 (SiCl c M d) Cl m M n] 2 [Si 20 (SiCl a M b) 10 (SiCl c M d) 2 Cl m M n]
(Where, a + b = 3, a = 0-3, b = 0-3, c + d = 2, c = 0-2, d = 0-2, m + n = 45, m = 1-45, n = 0 44)
It is represented by the chemical formula In the formula (1), the part (SiCl a M b ) f represents a terminal site of the polymer that is not involved in the polymerization reaction.
本発明の［２０］シラフラーラン骨格を有する塩素化物のユニットが（Ｓｉ−Ｓｉ）の結合で３つの前記ユニットが環状に結合した３量体は、
［Ｓｉ２０（ＳｉＣｌ２）２（ＳｉＣｌａＭｂ）１０ＣｌｍＭｎ］３
（式中、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４）
もしくは
［Ｓｉ２０（ＳｉＣｌａＭｂ）１０（ＳｉＣｌｃＭｄ）２ＣｌｍＭｎ］３
（式中、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、ｃ＋ｄ＝２、ｃ＝０〜２、ｄ＝０〜２、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４）
の化学式で表される。
The [20] chlorinated unit having a shirarahlaran skeleton of the present invention is a trimer in which three units are bonded in a cyclic manner with a bond of (Si-Si),
[Si 20 (SiCl 2) 2 (SiCl a M b) 10 Cl m M n] 3
(Where, a + b = 3, a = 0-3, b = 0-3, m + n = 45, m = 1-45, n = 0-44)
Or [Si 20 (SiCl a M b ) 10 (SiCl c M d) 2 Cl m M n] 3
(Where, a + b = 3, a = 0-3, b = 0-3, c + d = 2, c = 0-2, d = 0-2, m + n = 45, m = 1-45, n = 0 44)
It is represented by the chemical formula
以上、重合体として３量体までリニア型、環状型の例を示したが、前記一般式（１）で表される［２０］シラフラーラン骨格を有するユニットは、３２のＳｉのうち１２のＳｉが結合可能な活性なＳｉであり、立体障害がなければ前記ユニットは最大３６の結合末端でＳｉ同士の結合が可能である。従って、このようなＳｉ結合末端で、前記ユニットは重合して巨大な重合体を生成することが可能である。 As described above, examples of the linear type and the cyclic type up to the trimer are shown as the polymer. However, the unit having the [20] shirarahralane skeleton represented by the general formula (1) has 12 Si out of 32 It is an active Si that can be bonded, and if there is no steric hindrance, the unit can bond Si at a maximum of 36 bond ends. Therefore, at such Si bond ends, the unit can polymerize to form a huge polymer.
続いて、本発明の［２０］シラフラーラン骨格を複数個有する塩素化物の重合体の製造方法について説明する。
本発明の［２０］シラフラーラン骨格を複数個有する塩素化物の重合体の製造方法は、有機溶媒中、［２０］シラフラーラン塩素化物と反応剤を−８０℃から２５０℃の範囲で混合させることでシラフラーラン骨格を複数個有する塩素化物の重合体を製造することができる。好ましい製造方法として、不活性ガス雰囲気を提供できる実験設備において、密閉できる反応容器にシラフラーラン塩素化物、反応剤及び有機溶媒を入れ、撹拌することが挙げられる。
Subsequently, a method for producing a polymer of chlorinated product having a plurality of [20] shirafuraran skeletons of the present invention will be described.
The method for producing a polymer of chlorinated product having a plurality of [20] shirara lan skeletons according to the present invention comprises mixing [20] chloraline chlorinated product and a reactant in an organic solvent in the range of −80 ° C. to 250 ° C. A chlorinated polymer having a plurality of skeletons can be produced. As a preferable production method, in an experimental facility capable of providing an inert gas atmosphere, a chlorinated silane chloride, a reactant and an organic solvent are placed in a reaction vessel that can be sealed and stirred.
本発明の製法において、出発原料の［２０］シラフラーラン塩素化物は、［ｎ−Ｅｔ４Ｎ］［Ｓｉ３２Ｃｌ４５］ ・２ＳｉＣｌ４、［ＰＰｈ４］［Ｓｉ３２Ｃｌ４５］ ・ＣＨ２Ｃｌ２、［ｎ−Ｂｕ４Ｎ］［Ｓｉ３２Ｃｌ４５］ ・２ＣＨ２Ｃｌ２などがあるが、出発原料として［ｎ−Ｂｕ４Ｎ］［Ｓｉ３２Ｃｌ４５］ ・２ＣＨ２Ｃｌ２が好ましい。 In the production method of the present invention, the starting raw material [20] chloralane chlorinated product is [n-Et 4 N] [Si 32 Cl 45 ] .2SiCl 4 , [PPh 4 ] [Si 32 Cl 45 ] .CH 2 Cl 2 , [N-Bu 4 N] [Si 32 Cl 45 ] · 2CH 2 Cl 2 and the like are available, but [n-Bu 4 N] [Si 32 Cl 45 ] · 2CH 2 Cl 2 is preferable as a starting material.
本発明に係る有機溶媒の例は、テトラヒドロフラン（ＴＨＦ）、１、４−ジオキサン、ジエチルエーテル、トルエン、メチルシクロヘキサン、クラウンエーテル、キシレン、トリメチルベンゼン、１、２、３、４−テトラヒドロナフタレン、ペンタン、ノルマルヘキサン、シクロヘキサン、１、２−ジメトキシエタン等が挙げられ、このうち１種単独、または２種以上を混合して用いてもよい。 Examples of the organic solvent according to the present invention are tetrahydrofuran (THF), 1,4-dioxane, diethyl ether, toluene, methylcyclohexane, crown ether, xylene, trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, pentane, Normal hexane, cyclohexane, 1,2-dimethoxyethane and the like can be mentioned. Among these, one kind may be used alone, or two or more kinds may be mixed and used.
本発明に係る反応剤は、アルカリ金属からなる群より少なくとも１種の金属を含む化合物を用いることができる。アルカリ金属を含む化合物の例としては、ナトリウム、リチウム、カリウム、カリウム−黒鉛、ナトリウム−カリウム合金、メチルリチウム、ノルマルブチルリチウム、セカンダリーブチルリチウム、ターシャリーブチルリチウム等が挙げられる。
これらアルカリ金属を含む化合物のうち１種単独、または２種以上を混合して反応剤として用いてもよい。
このような反応剤の量としては、０．０１ｍｏｌ％以上５００ｍｏｌ％であることが好ましい。
As the reactant according to the present invention, a compound containing at least one metal from the group consisting of alkali metals can be used. Examples of the compound containing an alkali metal include sodium, lithium, potassium, potassium-graphite, sodium-potassium alloy, methyl lithium, normal butyl lithium, secondary butyl lithium, tertiary butyl lithium and the like.
Among these compounds containing an alkali metal, one kind may be used alone, or two or more kinds may be mixed and used as a reactant.
The amount of such a reactant is preferably 0.01 mol% or more and 500 mol%.
本発明に係る実験設備は、不活性ガス循環装置精製装置のついた露点温度‐９０℃の実験設備、例えば不活性ガス循環装置グローブボックス内が好ましい。また反応剤に金属リチウムを用いる場合の不活性ガスはアルゴンガスがよい。 The experimental equipment according to the present invention is preferably an experimental equipment with a dew point temperature of −90 ° C. equipped with an inert gas circulation device purification apparatus, for example, an inert gas circulation device glove box. In addition, argon gas is preferable as the inert gas when metallic lithium is used as the reactant.
本発明に係る密閉できる反応容器の例は、バイアル瓶、シュレンク、フラスコ、試験管、テフロン（登録商標）内筒型密閉容器、テフロン（登録商標）内筒型反応装置、ポータブルリアクター、オートクレーブ、ＮＭＲ試験管等がある。 Examples of the reaction vessel that can be sealed according to the present invention include vials, Schlenk, flasks, test tubes, Teflon (registered trademark) inner cylindrical sealed containers, Teflon (registered trademark) inner cylindrical reactors, portable reactors, autoclaves, NMR There are test tubes.
本発明に係る攪拌方法の例は、スターラーバー、撹拌羽、振とう機、超音波等が挙げられる。 Examples of the stirring method according to the present invention include a stirrer bar, a stirring blade, a shaker, and an ultrasonic wave.
反応条件としては、反応温度は−８０℃〜２５０℃であることが好ましい。また、室温〜１２０℃であることがより好ましい。反応条件として反応時間は１０分以上であることが好ましい。 As reaction conditions, the reaction temperature is preferably -80 ° C to 250 ° C. Moreover, it is more preferable that it is room temperature-120 degreeC. As reaction conditions, the reaction time is preferably 10 minutes or more.
（２９Ｓｉ−ＮＭＲの測定）
２９Ｓｉ−ＮＭＲは（装置名：ＪＮＭ−ＥＣＡ４００（ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ 製）、溶媒：ＴＨＦ−ｄ８、４００ＭＨｚ）を用いて測定した。
(Measurement of 29 Si-NMR)
29 Si-NMR was measured using (apparatus name: JNM-ECA400 (manufactured by JEOL RESONANCE), solvent: THF-d 8 , 400 MHz).
［ｎ−Ｂｕ４Ｎ］［Ｓｉ３２Ｃｌ４５］の合成
露点温度−９０℃のアルゴンガス循環装置のついたグローブボックス内で密閉のできるナスフラスコにテトラブチルアンモニウムクロライド２．５０１０ｇ、トリブチルアンモニウム１．２ｍｌ、ジクロロメタン２２．５ｍｌを室温で仕込んだ。１０分撹拌後、ヘキサクロロジジラン２５．６１２６ｇ添加し、２日間室温で撹拌した。２日後、析出物をろ過し、ろ液を１週間静置した。１週間後、デカントにより上澄みを除去し、５ｍｌのジクロロメタンを加え、さらにデカントした。この操作を４回繰り返し、得られた白色固体を乾燥させることで目的の［ｎ−Ｂｕ４Ｎ］［Ｓｉ３２Ｃｌ４５］・２ＣＨ２Ｃｌ２を０．３７７６ｇ（収率１．４％）を合成した。
Synthesis of [n-Bu 4 N] [Si 32 Cl 45 ] In a eggplant flask which can be sealed in a glove box equipped with an argon gas circulation device having a dew point temperature of −90 ° C., 2.5010 g of tetrabutylammonium chloride, 1. 2 ml and 22.5 ml of dichloromethane were charged at room temperature. After stirring for 10 minutes, 25.6126 g of hexachlorodizirane was added and stirred at room temperature for 2 days. Two days later, the precipitate was filtered, and the filtrate was allowed to stand for 1 week. One week later, the supernatant was removed by decanting, 5 ml of dichloromethane was added, and decanting was performed. This operation was repeated four times, and the obtained white solid was dried to obtain 0.3776 g (yield: 1.4%) of the desired [n-Bu 4 N] [Si 32 Cl 45 ] · 2CH 2 Cl 2. Synthesized.
２９Ｓｉ−ＮＭＲ（４００ＭＨｚ、ＴＨＦ−ｄ８）：δ＝３１．１、１０．４、−６０．２ｐｐｍ． 29 Si-NMR (400 MHz, THF-d 8 ): δ = 31.1, 10.4, −60.2 ppm.
（実施例１）
露点温度‐９０℃のアルゴンガス循環装置のついたグローブボックス内でＮＭＲ試験管に ［ｎ−Ｂｕ４Ｎ］［Ｓｉ３２Ｃｌ４５］ ・２ＣＨ２Ｃｌ２を０．２０１５ｇ入れ、ＴＨＦ−ｄ８を０．４ｍｌ仕込んだ後、金属リチウム０．０２４４ｇを添加し、振とう機を用いて撹拌した。１日後、２９Ｓｉ−ＮＭＲを測定した結果、原料の２９Ｓｉ−ＮＭＲと比較して新たにδ＝−１９．０ｐｐｍの化学シフトを観測した。分子中に（−ＳｉＣｌ２−ＳｉＣｌ２−）構造を有する［ｎ−Ｂｕ４Ｎ］２［Ｓｉ６Ｃｌ１４］の２９Ｓｉ−ＮＭＲの化学シフトはδ＝−２１．７ｐｐｍ（非特許文献４）と報告されている。このことから、δ＝−１９．０ｐｐｍの化学シフトは［２０］シラフラーラン骨格を有する塩素化物の末端基（ＳｉＣｌ３）どうしが結合し、新たに−ＳｉＣｌ２−ＳｉＣｌ２−結合が形成したことに由来するピークと考えられる。原料のシラフラーラン骨格を構成しているＳｉＣｌ３基の直接結合しているＳｉの化学シフトが−６０．２ｐｐｍから−５２．２ｐｐｍに低磁場シフトしている。これは得られた化合物の化学的環境の変化があったため、即ち化合物の構造変換が起きていることを示している。また、シラフラーラン骨格が分解した場合、ＳｉＣｌ３基が直接結合しているシラフラーラン骨格のＳｉ（−５０ｐｐｍ〜―６０ｐｐｍ付近）とＳｉＣｌ３基が結合していないシラフラーラン骨格を有するＳｉ−Ｃｌ結合（３０ｐｐｍ付近）に由来するピークが消えてしまうが、相当するピークが観測された。このことから［２０］シラフラーラン骨格を複数個有する塩素化物の重合体が生成したと判断した。
Example 1
In a glove box equipped with an argon gas circulation device with a dew point temperature of -90 ° C, 0.2015 g of [n-Bu 4 N] [Si 32 Cl 45 ] · 2CH 2 Cl 2 is placed in an NMR test tube, and THF-d 8 is added. After charging 0.4 ml, 0.0244 g of metallic lithium was added and stirred using a shaker. One day later, 29 Si-NMR was measured, and as a result, a chemical shift of δ = −19.0 ppm was newly observed as compared with the raw material 29 Si-NMR. The chemical shift of 29 Si-NMR of [n-Bu 4 N] 2 [Si 6 Cl 14 ] having a (—SiCl 2 —SiCl 2 —) structure in the molecule is δ = −21.7 ppm (Non-patent Document 4) It is reported. From this, the chemical shift of δ = −19.0 ppm is that the end groups (SiCl 3 ) of chlorinated compounds having a [20] shirarahralane skeleton are bonded to each other, and a new —SiCl 2 —SiCl 2 — bond is formed. It is thought to be the peak derived from. The chemical shift of Si, which is directly bonded to the SiCl 3 group constituting the Shirararan skeleton of the raw material, is shifted from -60.2 ppm to -52.2 ppm by a low magnetic field. This indicates that the chemical environment of the obtained compound has changed, that is, the structural transformation of the compound has occurred. In addition, when the Shirara lan skeleton is decomposed, Si of the Shirara lane skeleton to which the SiCl 3 group is directly bonded (-50 ppm to -60 ppm) and a Si-Cl bond (about 30 ppm) having the Shirara lane skeleton to which the SiCl 3 group is not bonded. ) Disappeared, but the corresponding peak was observed. From this, it was judged that a polymer of [20] chlorinated product having a plurality of shirauraran skeletons was formed.
２９Ｓｉ−ＮＭＲ（４００ＭＨｚ、ＴＨＦ−ｄ８）：δ＝３０．３、２０．１〜１０．０、−１９．０、−５２．２ｐｐｍ． 29 Si-NMR (400 MHz, THF-d 8 ): δ = 30.3, 20.1-10.0, −19.0, −52.2 ppm.
以上のような本発明の［２０］シラフラーラン骨格を有する塩素化物の複数個からなる重合体は、リチウムイオン電池負極材、キャパシタ材料、太陽電池、半導体、生体イメージング材料、光学材料等の分野に応用できる可能性がある。
The polymer composed of a plurality of chlorinated compounds having the [20] shirarahralane skeleton of the present invention as described above is applied to the fields of lithium ion battery negative electrode materials, capacitor materials, solar cells, semiconductors, bioimaging materials, optical materials and the like. There is a possibility.
Claims (5)
［Ｓｉ２０（ＳｉＣｌ２）ｅ（ＳｉＣｌａＭｂ）ｆ（ＳｉＣｌｃＭｄ）ｇＣｌｍＭｎ］ （１）
（前記式（１）中、Ｍはアルカリ金属、１２≧ｅ≧０、ａ＋ｂ＝３、ａ＝０〜３、ｂ＝０〜３、１１≧ｆ≧０、ｃ＋ｄ＝２、ｃ＝０〜２、ｄ＝０〜２、１２≧ｇ≧０、ｅ＋ｆ＋ｇ＝１２、ｍ＋ｎ＝４５、ｍ＝１〜４５、ｎ＝０〜４４の整数を示す。） [20] A polymer of a chlorinated product having a silaflalan skeleton, characterized in that it has at least two units having a [20] silaflalan skeleton represented by the following general formula (1).
[Si 20 (SiCl 2) e (SiCl a M b) f (SiCl c M d) g Cl m M n] (1)
(In the formula (1), M is an alkali metal, 12 ≧ e ≧ 0, a + b = 3, a = 0-3, b = 0-3, 11 ≧ f ≧ 0, c + d = 2, c = 0-2. D = 0-2, 12 ≧ g ≧ 0, e + f + g = 12, m + n = 45, m = 1-45, n = 0-44.
The organic solvent is tetrahydrofuran (THF), 1,4-dioxane, diethyl ether, toluene, methylcyclohexane, crown ether, xylene, trimethylbenzene, 1,2,3,4-tetrahydronaphthalene, pentane, normal hexane, cyclohexane, 1 The method for producing a polymer of a chlorinated product having a shirahararan skeleton according to any one of claims 2 to 4, which is an organic solvent containing at least one kind from 2-dimethoxyethane.
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