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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

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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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Step-Growth Polymerization: Overview01:03

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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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Radical Chain-Growth Polymerization: Mechanism01:09

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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 species into...
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Radical Chain-Growth Polymerization: Overview01:10

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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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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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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Directional Supramolecular Polymerization in a Dynamic Microsolution: A Linearly Moving Polymer's End Striking

Shota Matoba1, Chisako Kanzaki1, Kae Yamashita1

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Journal of the American Chemical Society
|June 1, 2021
PubMed
Summary
This summary is machine-generated.

Researchers developed a method for directional supramolecular polymerization using perylene bisimide (PBI) monomers. Shear force in microflow channels selectively activates one end of the growing polymer, enabling controlled growth and block copolymer synthesis.

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Polymer Chemistry

Background:

  • Directional chain reactions are common in nature but challenging in artificial self-assembly.
  • Existing artificial one-dimensional self-assembling systems lack controlled directional growth.

Purpose of the Study:

  • To develop a system for directional supramolecular polymerization using perylene bisimide (PBI) derivatives.
  • To investigate the role of shear force in controlling polymer growth and enabling block copolymer synthesis.

Main Methods:

  • Utilized perylene bisimide (PBI) derivatives as monomers in a microflow channel system.
  • Investigated nucleation and growth dynamics under varying flow rates and shear stress.
  • Employed in situ fluorescence spectra and linear dichroism to monitor polymerization.
  • Applied the strategy to a two-monomer system for diblock copolymer formation.

Main Results:

  • Spontaneous nucleation of PBI monomers was induced, facilitated by shear force.
  • Shear stress selectively accelerated polymer growth at one end of oriented polymers.
  • Directional growth predominated over free monomer nucleation.
  • A diblock copolymer was successfully synthesized through selective reaction at the polymer terminus, forming a molecular heterojunction.

Conclusions:

  • Friction-induced activation of a single polymer end enables directional supramolecular polymerization.
  • This strategy is broadly applicable to directional supramolecular block copolymerizations.
  • Allows for the precise formation of molecular heterojunctions in polymers.