JP2018536029A - 微粒子アルカリ金属分散体との反応のための連続方法 - Google Patents
微粒子アルカリ金属分散体との反応のための連続方法 Download PDFInfo
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Abstract
Description
本発明の方法に関し、一官能基の、二官能基の、三官能基の、及び多官能基の(mono−,di−,tri− und polyfunktionelle)ハロゲン化アルキル(アルキルハライド)及びハロゲン化アリール(アリールハライド)、並びにそれらの混合物、及び、一官能基の、二官能基の、三官能基の、及び多官能基のハロオルガノシラン(polyfunktionelle Halogenorganosilane)及びそれらの混合物、のようなウルツ・カップリングに対して、共通の全ての基材を反応させることができる。ハロゲン化合物において、前記ハロゲンとしては、フッ素、塩素、臭素、及びびヨウ素を使用することができ、特に、塩素、臭素、及びヨウ素を使用することができ、好ましくは、塩素及び臭素を使用することができる。特に、本発明は、ポリシランではないハロゲン化されたオルガノシラン構成要素のポリカルボシラン及びポリシランの調製のために適している。ハロゲン化されたオルガノシラン成分は、5個未満のケイ素原子、好ましくは3個までのケイ素原子、より好ましくは2個以下のケイ素原子、及び最も好ましくは1個だけのケイ素原子を含むことによって規定される。
実施された反応のために、3つのターンテーブル及び一体化された熱交換器を備えた市販のFlowid社(the Company Flowid)のスピンプロ・リアクター(SpinPro Reactor)を使用した。(アイントホーフェン(Eindhoven)、オランダ(Netherlands)、http://www.flowid.nl/spinpro−reactor/)。ターンテーブルと壁との間の距離は2mmであった。リアクター容積は230mlであった。すべての反応に対して、リアクターは、不活性化のために20回排気され、8バールの窒素で換気した。ポリシラン(実験例1及び2)の合成のために、20分間の滞留時間でもって(流速7.2kg/h = 2.8L;流速10.8kg/h => 4.1L)連続撹拌タンクは、滞留時間ユニットとしてSDRの下流側に接続された。
[ポリ(メチルフェニルシラン)の調製のためのセミバッチ・プロセス:]
標準的なシュレンク技術(Standard−Schlenk−Technik)を用いて、滴下漏斗、還流冷却器、KPG撹拌機、及び温度プローブを備えた1000mLの四ツ口フラスコを含む装置は、排気され、アルゴンで満たされた。四ツ口フラスコ内に、215gのキシレン及び17.9gのナトリウムが充填された。滴下漏斗はまた、不活性ガス雰囲気下において、67.3gのジクロロメチルフェニルシランで満たされた。ゆっくり攪拌しながら、ナトリウムが溶融するように、フラスコはオイルバス中で約102℃に加熱された。ここで、攪拌速度を正確に300rpmに設定し、約5分間撹拌が実施された。この後、均質で微細に分割された分散体が形成された(目視評価)。この懸濁液に、ジクロロフェニルメチルシランが約30分間かけて計量供給された。反応の開始は、反応混合物の強い紫色の着色だけでなく、温度における上昇によっても、観察され得た。反応温度が常に102から106℃の温度範囲内に保たれるところ、ジクロロフェニルメチルシランが計量供給時間にわたって均一に添加されるように、計量供給速度は選択された。
モル質量:2000g/モル
1H NMR(δ[ppm]、CDCl3):6.5−7.5ppm、0.5ppm
13C NMR(δ[ppm]、CDCl3):134−138ppm、125−130ppm、21ppm
29Si−NMR(δ[ppm]、CDCl3):−41ppm、−40ppm、−39ppm、+15ppm
反応を開始させるために、SDRは、回転速度を1000又は2500rpmに、加熱オイル温度を100又は105℃に、そして、初期キシレン流速を6.5kg/hに、調整された。リアクター内で一定の温度が確立されたら、ナトリウム計量供給が開始された。収集容器内へと灰色の分散液の放出が観察されるとすぐに、ジクロロメチルフェニルシランの計量供給が開始された。ジクロロメチルフェニルシラン対ナトリウムの質量比は、すべての実験において5/1で一定であった。反応の開始は、リアクターの第1及び第2のプレート上の温度上昇によって直ちに認識された。その後、深く紫色に呈色した反応混合物は、収集容器内へと排出された。計量供給速度及びオイル温度は、表にリストされているように、変化させた。
13C NMR(δ[ppm]、CDCl3):134−138ppm、125−130ppm、21ppm
29Si−NMR(δ[ppm]、CDCl3):−41ppm、−40ppm、−39ppm、+15ppm
2500rpmの回転速度、125℃の加熱オイル温度、及び6.5kg/hのキシレン流速で、ナトリウム計量供給が、2g/分で開始された。リアクター内の温度は、122℃で平準化された。リアクターからの灰色の分散液の放出が観察されるとすぐに、モノマー計量供給が、10g/分で開始された。反応の開始は、第1のプレート上の129℃までのリアクター内の温度上昇によって直ちに認識された。少し後に、濃い紫色に呈色した反応混合物は、収集容器内へと排出された。生成物は、窒素下で濾過され、そして、溶媒は留去された。ポリマーは、1H NMR、13C NMR、29Si NMR分光法(それぞれC6D6中)及びゲル浸透クロマトグラフィー(THF中、光散乱検出器を用いて)によって特徴付けられた。
13C NMR(δ[ppm]、CDCl3):134−138ppm、125−130ppm、21ppm
29Si−NMR(δ[ppm]、CDCl3):−41ppm、−40ppm、−39ppm、+15ppm
2500rpmの回転速度、110℃のオイル温度、及び6.5kg/hのキシレン流速で、ナトリウム計量供給は、1.0g/分で開始された。リアクター内の温度は、122℃で平準化された。リアクターからの灰色の分散液の放出が観察されるとすぐに、1,6−ジブロモヘキサンの計量供給が、4g/分で開始された。反応の開始は、第1のプレート上の127℃までのリアクター内の温度上昇によって直ちに認識された。少し後に、濃い紫色に呈色した反応混合物が、収集容器内へと排出された。生成物は、窒素下で濾過して分離され、濾液の組成は、GC−MSによって分析され、98.5%の変換率が、決定された。純粋な生成物は、91%の収率において濾液の分別蒸留によって得られ、そして、1H及び13C NMR分光法により解析された。
1H NMR(δ[ppm]、CDCl3):1.44
13C NMR(δ[ppm]、CDCl3):26.9
Claims (10)
- 不活性溶媒中において微細に分割されたアルカリ金属の分散液の変換のための連続化学反応を実施するための装置の使用。
- 回転ディスク・リアクターが前記装置として使用されることを特徴とする、請求項1の使用。
- リチウム、ナトリウム、カリウム、それらの混合物及び/又はそれらの合金が、前記アルカリ金属として使用されることを特徴とする、請求項1又は2に記載の使用。
- 化学プロセスがウルツ合成であることを特徴とする、請求項1から3のいずれかに記載の使用。
- 主族第IV族の元素の一官能基の、二官能基の、又は多官能基の(mono−,di− oder multifunktionellen)ハロゲン化合物が、前記ウルツ合成のための反応物として使用されることを特徴とする、請求項4に記載の使用。
- ウルツ合成において、一官能基の、二官能基の、又は多官能基の(mono−,di− oder multifunktionellen)有機ハロゲン化合物及びそれらの混合物から、直鎖状、分枝状、及び環状の炭化水素を調製するための、請求項4又は5に記載の使用。
- 一官能基の、二官能基の、又は多官能基の(mono−,di− oder multifunktionellen)ハロシラン及びそれらの混合物から、ポリシラン、特にポリカルボシランを調製するための、請求項5又は6に記載の使用。
- 化学プロセスがアシロイン縮合であることを特徴とする、請求項1から3のいずれかに記載の使用。
- 有機モノエステル化合物、ジエステル化合物、トリエステル化合物、又はポリエステル化合物が、前記アシロイン縮合のための反応物として使用されることを特徴とする、請求項8に記載の使用。
- 前記回転ディスク・リアクターが、その下流側に接続された滞留時間ユニットを有することを特徴とする、請求項1から9のいずれかに記載の使用。
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