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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 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...
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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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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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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...
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Covalent on-surface polymerization.

Leonhard Grill1, Stefan Hecht2,3,4,5

  • 1Physical Chemistry Department, University of Graz, Graz, Austria. leonhard.grill@uni-graz.at.

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On-surface polymerization enables the creation of novel polymers with unique structures and properties not possible in solution. This review overviews covalent on-surface polymerization, its mechanisms, and future challenges.

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Area of Science:

  • Materials Science
  • Surface Chemistry
  • Polymer Chemistry

Background:

  • Scanning probe microscopy allows atomic-level study of surface polymerization.
  • Surface confinement enables formation of unique polymers not accessible in solution.
  • Covalent on-surface polymerization has been studied for over a decade.

Purpose of the Study:

  • To provide an overview of on-surface polymerization.
  • To analyze crucial aspects, mechanisms, kinetics, and thermodynamics.
  • To reflect on the current status and future prospects of the field.

Main Methods:

  • Review of existing literature on on-surface polymerization.
  • Analysis of fundamental mechanisms, kinetics, and thermodynamics.
  • Highlighting examples of locally induced polymerization.

Main Results:

  • Surfaces play a critical role in controlling polymer structure, dimensionality, and composition.
  • On-surface polymerization allows for the formation of unprecedented polymer architectures.
  • The field has advanced significantly in understanding and controlling these processes.

Conclusions:

  • On-surface polymerization is a powerful technique for creating novel materials.
  • Understanding surface-polymer interactions is key to controlling polymer formation.
  • Future research should focus on addressing current scientific challenges and exploring new possibilities.