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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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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...
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Characteristics and Nomenclature of Copolymers01:24

Characteristics and Nomenclature of Copolymers

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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
2.5K
Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

2.4K
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...
2.4K
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

7.8K
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.
7.8K
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

1.9K
The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
1.9K
Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

3.4K
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...
3.4K

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Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
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精密定義されたマルチブロック共ポリマーの固体相合成

Grzegorz Szczepaniak1,2, Kriti Kapil1, Samuel Adida1

  • 1Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.

Journal of the American Chemical Society
|July 30, 2024
PubMed
まとめ

この研究では,配列制御ブロック共ポリマーを作るためのアンフィフィリックChemMatrix樹脂と原子移転基ポリメリゼーション (ATRP) を使用した新しい固相ポリマー合成法が導入されています.

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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

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Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst
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Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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科学分野:

  • ポリマー化学
  • 材料科学
  • 有機合成

背景:

  • 固体相合成はペプチド化学から生じ,マクロモレキュルの強力な技術である.
  • 伝統的な固体支柱は,溶媒の互換性や処理に制限があります.

研究 の 目的:

  • 配列制御されたポリマー合成のための効率的な固体相法を開発する.
  • 化学マトリックス (CM) 樹脂のユニークな特性を活用し,ポリマー合成を改善する.

主な方法:

  • ポリエチレングリコール (PEG) 基のChemMatrix (CM) 樹脂に対するポリマー鎖の共性固定.
  • 原子移転ラジカルポリメリゼーション (ATRP) と固体相技術の組み合わせ
  • マルチブロック共ポリマー (di-, tri-, tetra-, penta-block) の合成

主要な成果:

  • 分子重量と分散制御の優れた,明確に定義されたブロックコポリマーの高収量を達成した.
  • 有機および水性媒体の様々なモノマーで方法の汎用性を実証した.
  • 樹脂の毛穴の閉じ込めにより,非常に高い分子量を達成する際の制限を特定した.

結論:

  • CM樹脂を用いた開発された固相ポリマー合成アプローチは,配列制御ブロックコポリマーを作るのに有効です.
  • この方法は,多様な機能を持つ,個別化されたブロックコポリマーを合成するための,簡素化され,迅速な経路を提供します.
  • CM樹脂のアンフィフィリックな性質は,従来のサポートと比較して処理効率を高めます.