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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Anionic Chain-Growth Polymerization: Overview01:20

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Cationic Chain-Growth Polymerization: Mechanism00:57

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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オキシムベースの,触媒のないダイナミックコバルントポリウレタン

Wen-Xing Liu1,2, Chi Zhang3, Huan Zhang1,2

  • 1Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, China.

Journal of the American Chemical Society
|May 31, 2017
PubMed
まとめ

この研究は,新しいダイナミックなポリマークラスであるポリオキシムウレタン (POU) を導入する. これらのポリマーは,従来のポリウレタンの限界を克服し,優れた機械的性質を持つ,触媒のない,治癒しやすい,再利用可能な材料を提供します.

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科学分野:

  • ポリマー化学
  • 材料科学
  • 有機化学

背景:

  • ポリウレタン (PU) は広く使用されているが,有毒な触媒と熱固体の劣悪な処理能力のために制限に直面している.
  • 先進的な材料の応用には,従来のPUの持続可能で加工可能な代替品の開発が不可欠です.

研究 の 目的:

  • ダイナミックな共性ポリマーであるポリオキシムウレタン (POU) の新種を合成し,特徴づけること.
  • POUの触媒なしの合成,熱的可逆性,および機械的性質を調査する.
  • 伝統的なポリウレタンの持続可能な代替品としてのPOUの可能性を調査する.

主な方法:

  • 多機能オキシメスとヘクサメチレンジイソシアネート (HDI) の未触媒ポリ添加
  • ディクロロメタン (DCM) を含む様々な溶媒での運動学的研究により,最適なポリメリゼーション条件を決定する.
  • 熱安定性および可逆性を評価するための熱重量測定分析と動的機械分析.
  • 反応メカニズムを解明するための密度関数理論 (DFT) の計算.

主要な成果:

  • DCMで30 °Cで3時間で高ポリメリゼーション変換 (∼99%) を達成し,線形POUを生成する.
  • 解離メカニズムによって約100°Cで熱逆性オキシム-カルバマート結合が実証されている.
  • クロスリンクされたPOUは,触媒なしで治癒し,リサイクルできる性質を示した.
  • DFT計算では,オキシムのニトロンタウトメアは急速なポリメリゼーションと熱可逆性を媒介していることが示された.

結論:

  • ポリオキシムウレタン (POU) は,ダイナミックな共性ポリマーの有望な新種である.
  • POUは,容易で触媒のない調製,優れた機械性能,およびダイナミックな特性 (治癒性/リサイクル性) を提供しています.
  • POUのユニークな性質は,ニトロンタウトメアによって媒介される可逆性オキシム-カルバメート結合から生じ,持続可能な材料開発の道を開く.