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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

2.7K
Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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...
2.4K
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

2.8K
The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
2.8K
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

8.3K
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
8.3K
Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
3.7K
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

3.5K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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RAFTポリメリゼーションの逆転:触媒のないデポリメリゼーションアプローチによるほぼ定量的なモノマー生成

Hyun Suk Wang1, Nghia P Truong1, Zhipeng Pei2

  • 1Laboratory of Polymeric Materials, Department of Materials, ETH Zurich, Vladimir-Prelog-Weg 5, Zurich 8093, Switzerland.

Journal of the American Chemical Society
|February 25, 2022
PubMed
まとめ

研究者はポリメタクリレットを脱ポリマー化し,モノマーを再生するための触媒のない方法を開発しました. リバーシブル・ラジカル・ポリメリゼーションにおけるこの突破は,ポリマー再構築や新しいゲル形成を可能にし,ポリマー科学の応用を進めています.

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科学分野:

  • ポリマー化学
  • 材料科学
  • 有機化学

背景:

  • 制御された根性ポリメリゼーションの逆転とモノメアの再生は,ポリマーの研究と応用にとって極めて重要です.
  • ポリメタクリラートの効率的で触媒のないデポリメリゼーションを達成することは大きな課題でした.

研究 の 目的:

  • 多種多様なポリメタクリレットの新しく,高効率で,触媒のないデポリメリゼーション方法について報告する.
  • ポリマー再構築と新材料合成のための脱ポリマー化製品の有用性を実証する.

主な方法:

  • 高エンドグループフィデリティを持つポリメタクリレットを合成するために,可逆的な加法-断片化-連鎖移転 (RAFT) ポリメリゼーションを使用した.
  • 熱条件 (120 °C) を適用して,鎖末端のラジカルを生成し,急速なデポリメリゼーション ("解凍") プロセスを開始します.
  • 線形,重量,交結,機能性ポリメタクリレットの脱ポリメリゼーションを調査し,ポリ (メチルメタクリレート) とポリ (オリゴ (エチレングリコール) メチルエーテルメタクリレートを含む.

主要な成果:

  • 多種多様なポリメタクリレットのほぼ定量的な (最大92%) 脱ポリメリゼーションを達成した.
  • 脱ポリマー化製品からの線形ポリマーの再構築を成功裏に実証した.
  • 脱ポリマー化された材料から新型の不溶性ゲルを作り出し,それも脱ポリマー化が可能でした.

結論:

  • 開発されたデポリメリゼーション方法は,制御された根性ポリメリゼーションで合成されたポリマーの能力を大幅に拡張します.
  • この研究はポリマー脱ポリマー化の限界を押し広げ 興味深い機械的洞察を明らかにしています
  • この発見により,ポリマーリサイクル,合成,高度な材料開発の新たな応用が可能になります.