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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.2K
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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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
3.5K
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

2.0K
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...
2.0K
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
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

2.5K
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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Polymers02:34

Polymers

34.8K
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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Updated: Jun 1, 2025

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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Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization.

Wentao Yu1, Zhiyao Yang1, Chengkan Yu1

  • 1College of Chemistry, Sichuan University, Chengdu 610064, China.

Beilstein Journal of Organic Chemistry
|January 21, 2025
PubMed
Summary

Researchers developed a new method for creating orthogonal supramolecular polymers using shape-persistent macrocycles. This approach expands the toolkit for designing advanced functional materials through noncovalent interactions.

Keywords:
hydrogen-bonded macrocycleorthogonal self-assemblyshape-persistentsupramolecular polymer

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Area of Science:

  • Supramolecular Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Orthogonal self-assembly is key for creating supramolecular polymers using AA- and AB-type monomers.
  • Current designs predominantly use 3D macrocycles; 2D shape-persistent macrocycles are less explored for this purpose.

Purpose of the Study:

  • To demonstrate a novel dimerization motif using hydrogen-bonded macrocycles for orthogonal supramolecular polymerization.
  • To expand the use of 2D shape-persistent macrocycles in supramolecular polymer construction.

Main Methods:

  • Utilized a hydrogen-bonded macrocycle as a dimerization motif.
  • Confirmed macrocycle-mediated connectivity via single-crystal X-ray diffraction.
  • Induced orthogonal polymerization using zinc ions, a macrocycle, and a terpyridinium derivative, analyzed by 1H NMR, DLS, and TEM.

Main Results:

  • A unique 2:2 host-guest binding motif was observed, mediated by pyridinium end groups through pi-stacking and other forces.
  • Successful orthogonal polymerization was achieved and characterized.
  • Viscosity measurements indicated a transition from oligomers to polymers at a critical concentration of 17 μM, showing high concentration dependence.

Conclusions:

  • A new dimerization motif based on shape-persistent, hydrogen-bonded macrocycles was established for orthogonal supramolecular polymers.
  • This work broadens the range of noncovalent building blocks for supramolecular chemistry.
  • The findings support the future development of novel functional materials.