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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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Radical Chain-Growth Polymerization: Mechanism01:09

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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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Anionic Chain-Growth Polymerization: Mechanism01:04

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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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Radical Chain-Growth Polymerization: Overview01:10

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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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Restarting Stalled Replication Forks02:37

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DNA replication is initiated at sites containing predefined DNA sequences known as origins of replication. DNA is unwound at these sites by the minichromosome maintenance (MCM) helicase and other factors such as Cdc45 and the associated GINS complex.The unwound single strands are protected by replication protein A (RPA) until DNA polymerase starts synthesizing DNA at the 5’ end of the strand in the same direction as the replication fork. To prevent the replication fork from falling apart,...
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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,...
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Initiators for Continuous Activator Regeneration (ICAR) Depolymerization.

Glen R Jones1, Maria-Nefeli Antonopoulou1, Nghia P Truong1

  • 1Laboratory for Polymeric Materials, Department of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093 Zürich, Switzerland.

Journal of the American Chemical Society
|December 12, 2024
PubMed
Summary
This summary is machine-generated.

Initiators for continuous activator regeneration (ICAR) depolymerization significantly lowers reaction temperatures for atom transfer radical polymerization (ATRP) polymer recycling. This method achieves high monomer yields at 120 °C, reducing energy consumption and side reactions.

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Area of Science:

  • Polymer Chemistry
  • Sustainable Chemistry
  • Chemical Engineering

Background:

  • Chemical recycling of atom transfer radical polymerization (ATRP) polymers requires high temperatures (170 °C).
  • High temperatures lead to energy inefficiency and reduced depolymerization yields due to end-group degradation.
  • Existing methods lack efficiency and broad applicability for ATRP polymer recycling.

Purpose of the Study:

  • Introduce initiators for continuous activator regeneration (ICAR) depolymerization as a low-temperature recycling method for ATRP polymers.
  • Demonstrate the efficiency and versatility of ICAR depolymerization.
  • Reduce energy consumption and side reactions in polymer recycling.

Main Methods:

  • Utilized commercially available free radical initiators to enable continuous activator regeneration.
  • Applied ICAR depolymerization to ATRP-synthesized polymers.
  • Investigated depolymerization efficiency, reaction temperatures, and side reactions through incubation studies.
  • Tested compatibility with different polymer end-groups (chlorine, bromine) and catalysts (copper, iron).

Main Results:

  • Achieved 96% depolymerization efficiency at 120 °C, a significant reduction from traditional methods.
  • ICAR depolymerization conversions are comparable to thermal reversible addition-fragmentation chain transfer (RAFT) depolymerizations.
  • Eliminated deleterious side reactions at milder temperatures.
  • Demonstrated successful depolymerization of both chlorine and bromine-terminated polymers with copper and iron catalysts.
  • Methodology was successfully scaled up to 1 gram.

Conclusions:

  • ICAR depolymerization offers a broadly applicable and efficient approach for low-temperature chemical recycling of ATRP polymers.
  • This method enhances sustainability by reducing energy input and improving yields.
  • ICAR depolymerization is robust, versatile, and compatible with various ATRP systems.