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サイクルポリマーの機械化学におけるダイナミック・メモリー効果
Yangju Lin1, Yudi Zhang1, Zi Wang1
1Department of Chemistry , Duke University , Durham , North Carolina 27708 , United States.
Journal of the American Chemical Society
|July 9, 2019
まとめ
ジェム・ジクロロプロパンメカノフォアを持つサイクルポリマーは,線形類似体と比較して活性化が低下している. これは,断片化中間物質は,機械化学的分裂中にその周期的起源の記憶を保持することを示唆している.
科学分野:
- ポリマー化学
- 機械化学
- 材料科学
背景:
- サイクルポリマーには独特の特性がありますが,その機械化学的行動は線形対比よりも理解されていません.
- ジェム・ジクロロプロパン (gDCC) ユニットは,機械的なストレス下でのポリマーチェーン分裂を可能にする効果的なメカノフォアとして機能します.
研究 の 目的:
- gDCCメカノフォールを含むサイクルポリマーのメカノ化学的振る舞いを,その線形アナログと比較する.
- 周期性ポリマーにおける鎖の断片化時のメカノフォール活性化 (Φ) の効率を決定する.
主な方法:
- リング拡張メタテシスポリメリゼーションによる複数のgDCCメカノフォアのサイクルポリマーの合成.
- パルス超音波を用いたポリマーメカノ化学の調査.
- オゾノリシスによるメカノケミカル製品の分析で活性化ゾーンを評価する.
主要な成果:
- サイクリックポリマーは,線形類似体と比較して,チェーン半減毎に活性化されたgDCCメカニコフォアの割合が低い (Φ = 0.38).
- オゾノリシスにより,線形ポリマーと比較して,連続性の低い機械化学活性化ゾーンが明らかになった.
- 周期性ポリマーの断片化は,同じイベント内でさらに分裂する線形中間物質を通して行われます.
結論:
- 周期性ポリマーにおけるメカノフォアの活性化が低下すると,断片化中に形成された線形中間物質は周期的な形状の記憶を保持していることが示唆される.
- この"記憶効果"は,後に起こる分裂に影響を及ぼし,当初線形だったポリマーと比較して連続性の低い活性化パターンを生み出します.
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