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Related Concept Videos

Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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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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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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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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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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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,...
2.2K
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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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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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...
3.5K
Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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Updated: Sep 21, 2025

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Emerging Trends in Polymerization-Induced Self-Assembly.

Nicholas J W Penfold1, Jonathan Yeow2, Cyrille Boyer2

  • 1Department of Chemistry, The University of Sheffield, Brook Hill, Sheffield, South Yorkshire, S3 7HF, United Kingdom.

ACS Macro Letters
|May 27, 2022
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Summary
This summary is machine-generated.

Polymerization-induced self-assembly (PISA) offers a versatile route to block copolymer nanoparticles. Alternative PISA methods provide enhanced control over nanoparticle morphology and functionality, enabling new applications.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Polymerization-induced self-assembly (PISA) is a key technique for synthesizing block copolymer nanoparticles.
  • Traditional PISA often relies on thermally initiated reversible addition-fragmentation chain transfer (RAFT) polymerization.
  • Existing methods offer limited control over nanoparticle morphology and functionality.

Purpose of the Study:

  • To review recent advancements in PISA for synthesizing block copolymer nanoparticles.
  • To highlight alternative PISA protocols beyond thermal RAFT polymerization.
  • To discuss improved control over copolymer morphology and functionality.

Main Methods:

  • Exploration of alternative PISA initiation methods (visible light, redox, enzymes).
  • Investigation of sequential PISA syntheses and postfunctionalization using external stimuli.
  • Optimization of PISA formulations via high-throughput polymerization and flow reactor studies.

Main Results:

  • Alternative PISA protocols enable enhanced control over nanoparticle morphology and functionality.
  • Sensitive monomers and biomolecules can be incorporated into nanoparticles.
  • Stimuli-responsive sequential syntheses and postfunctionalization (e.g., cross-linking) are achievable without purification.
  • High-throughput and flow reactor approaches facilitate PISA optimization and scale-up.

Conclusions:

  • Alternative PISA methods significantly expand the possibilities for rational block copolymer nanoparticle design.
  • The ability to incorporate sensitive components and perform sequential modifications opens new avenues for functional nanomaterials.
  • PISA is a powerful and scalable platform for creating diverse block copolymer nanostructures.