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Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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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...
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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
2.2K
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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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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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...
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Polymers02:34

Polymers

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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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ステレオ電子相互作用による超分子ポリマー組成の調節

Will R Henderson1, Guancen Liu1, Khalil A Abboud1

  • 1George & Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, P.O. Box 117200 Gainesville, Florida 32611-7200, United States.

Journal of the American Chemical Society
|August 4, 2021
PubMed
まとめ

新型ディシア[3.3]パラサイクロファンの超分子ポリメリゼーションは,アミド水素結合によって達成される. 硫黄を硫に酸化することで軌道相互作用が強化され,ポリマーの組立と伸縮が促進されます.

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科学分野:

  • 超分子化学
  • 有機化学
  • 材料科学

背景:

  • 超分子ポリメリゼーションは 調節可能な性質を持つ新しい材料への経路を提供します
  • 水素結合は自己組み立てを推進する 重要な非共性相互作用です
  • パラサイクロファンは分子設計のためのユニークな構造的支架を提供します.

研究 の 目的:

  • 2,11-ディシア[3.3]パラサイクロファンの超分子ポリメリゼーションを調査する.
  • ポリメリゼーションを推進する分子間および環間アミド水素結合の役割を明らかにする.
  • 立体電子効果,特に n → π* 相互作用がポリマー組立に与える影響を調査する.

主な方法:

  • 2,11-ディシア[3.3]パラサイクロファンの合成と特徴付け.
  • 水素結合とポリメリゼーションを研究するための光譜分析 (NMR,IR).
  • 構造変化を判別するX線結晶学
  • 電子相互作用とモデルシステムを調査するための計算化学 (DFT).

主要な成果:

  • 自己補完性アミド水素結合によって成功する 超分子ポリメリゼーション
  • ブリッジング硫黄原子を含む n → π* 相互作用の特定.
  • サルフォンへの酸化は n → π* 相互作用を強化し,ポリメリゼーションと伸縮を増加させます.
  • 実験的証拠 (延長定数,振動周波数,結晶学) はステレオ電子効果の役割を支持する.

結論:

  • 2,11-ジチア[3.3]パラサイクロファンは,アミド水素結合による超分子ポリメリゼーションを受けることができます.
  • n → π*の相互作用は組み立てに不可欠であり,硫黄酸化によって調節することができる.
  • ステレオ電子効果は,高分子ポリマー形成の効率と範囲を大きく影響する.