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Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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

Radical Chain-Growth Polymerization: Mechanism

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 the...
Hydrogen Bonds00:26

Hydrogen Bonds

Hydrogen BondsHydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.Hydrogen Bonds Control the World!Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are...
Hydrogen Bonds01:04

Hydrogen Bonds

A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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 generated carbocation,...
Stability of Conjugated Dienes01:28

Stability of Conjugated Dienes

Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.

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Updated: Jun 6, 2026

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
16:24

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

Published on: August 2, 2012

Chain stopper engineering for hydrogen bonded supramolecular polymers.

Thomas Pinault1, Bruno Andrioletti, Laurent Bouteiller

  • 1UPMC Université Paris 06, UMR 7610, Chimie des Polymères, F-75005 Paris, France.

Beilstein Journal of Organic Chemistry
|November 19, 2010
PubMed
Summary

Researchers explored new chain stoppers to control supramolecular polymer viscosity. Specific substituted ureas effectively reduced viscosity, with the best stopper featuring two hydrogen bond acceptors and no donors.

Keywords:
chain stoppergelhydrogen bondsupramolecular polymerurea

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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

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Last Updated: Jun 6, 2026

Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
07:28

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

Published on: November 27, 2015

Area of Science:

  • Supramolecular Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Supramolecular polymers are formed by self-assembly of monomers via non-covalent interactions.
  • The viscosity of supramolecular polymer solutions can be tuned using chain stoppers that cap the polymer ends.
  • Controlling viscosity is crucial for applications in gels and advanced materials.

Purpose of the Study:

  • To synthesize and evaluate novel substituted ureas and thioureas as chain stoppers for bis-urea based supramolecular polymers.
  • To understand the structure-property relationships governing the efficacy of these chain stoppers.
  • To identify optimal chain stopper designs for viscosity reduction.

Main Methods:

  • Synthesis of new substituted urea and thiourea compounds.
  • Characterization of synthesized compounds.
  • Viscosity measurements of supramolecular polymer solutions with varying chain stoppers.

Main Results:

  • The bis-thiourea analogue did not form a supramolecular polymer but acted as an effective chain stopper due to its hydrogen bonding characteristics.
  • All tested substituted ureas demonstrated a reduction in supramolecular polymer solution viscosity.
  • The most effective chain stopper featured two hydrogen bond acceptors in the monomer's position and lacked hydrogen bond donors.

Conclusions:

  • Substituted ureas are effective chain stoppers for bis-urea supramolecular polymers.
  • The design of chain stoppers, specifically the presence and position of hydrogen bond donors and acceptors, significantly impacts their performance.
  • Optimized chain stoppers offer a precise method for controlling the rheological properties of supramolecular polymer solutions.