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Related Concept Videos

Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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...
Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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 acceptor.
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...
Polymers02:34

Polymers

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 properties that they exhibit. Additionally,...
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,...

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Updated: Jun 23, 2026

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

Published on: February 7, 2017

Equilibrium polymerization models of re-entrant self-assembly.

Jacek Dudowicz1, Jack F Douglas, Karl F Freed

  • 1The James Franck Institute and the Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA. dudowicz@jfi.uchicago.edu

The Journal of Chemical Physics
|May 2, 2009
PubMed
Summary

This study explores re-entrant self-assembly, a phenomenon analogous to re-entrant phase separation. It demonstrates how competition between thermal activation and adsorption drives this complex self-assembly behavior.

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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Single-Molecule Diffusion and Assembly on Polymer-Crowded Lipid Membranes

Published on: July 19, 2022

Area of Science:

  • Thermodynamics and Materials Science
  • Polymer Chemistry and Self-Assembly

Background:

  • Liquid-liquid phase separation exhibits lower and upper critical solution temperatures.
  • Self-assembly transitions involve floor and ceiling temperatures based on concentration and temperature.
  • Some phase-separating systems display closed-loop phase boundaries with two critical points.

Purpose of the Study:

  • To analyze self-assembly analogs of re-entrant phase separation, termed re-entrant self-assembly.
  • To investigate the conditions under which re-entrant self-assembly occurs.

Main Methods:

  • Theoretical analysis of thermally activated equilibrium self-assembling systems.
  • Examination of self-assembly near an adsorbing boundary.

Main Results:

  • Re-entrant self-assembly transitions arise when thermal activation is more favorable than chain propagation.
  • Competition between adsorption and self-assembly near a boundary leads to re-entrant behavior.
  • Competition between interactions or equilibria underlies re-entrant behavior in both phase separation and self-assembly.

Conclusions:

  • Re-entrant self-assembly is a viable phenomenon in equilibrium self-assembling systems.
  • Understanding the interplay of different interactions is key to predicting re-entrant behavior.