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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.
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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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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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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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Controlling Exchange Pathways in Dynamic Supramolecular Polymers by Controlling Defects.

Anna L de Marco1,2, Davide Bochicchio1,2, Andrea Gardin3

  • 1Department of Innovative Technologies, University of Applied Sciences and Arts of Southern Switzerland, Polo Universitario Lugano, Campus Est, Via la Santa 1, 6962 Lugano-Viganello, Switzerland.

ACS Nano
|September 2, 2021
PubMed
Summary

Understanding monomer exchange in dynamic supramolecular polymers is key. Competition between directional and nondirectional interactions dictates exchange pathways, controlling fiber dynamics and defect formation.

Keywords:
coarse-grainingdefectsexchange pathwaysmolecular dynamicssupramolecular polymersunsupervised clustering

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Area of Science:

  • Supramolecular Chemistry
  • Polymer Science
  • Computational Chemistry

Background:

  • Supramolecular fibers self-assemble via noncovalent interactions, forming dynamic structures with continuous monomer exchange.
  • Understanding the molecular determinants of these exchange pathways is crucial but challenging.

Purpose of the Study:

  • To investigate the key factors controlling monomer exchange pathways in dynamic synthetic supramolecular polymers.
  • To elucidate how monomer interactions influence defect dynamics and overall fiber exchange mechanisms.

Main Methods:

  • Coarse-grained molecular modeling
  • Enhanced sampling techniques
  • Machine learning approaches

Main Results:

  • The competition between directional and nondirectional monomer interactions governs defect creation/annihilation.
  • Defects serve as the sites for monomer exchange within the supramolecular polymers.
  • Exchange pathways are determined by this interaction competition, influencing whether monomers exchange from fiber tips or along the entire length.

Conclusions:

  • The developed models provide a general framework for studying dynamic supramolecular assemblies.
  • Insights gained can guide molecular strategies to precisely control monomer exchange pathways in synthetic fibers.