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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.2K
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: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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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Base-Catalyzed Ring-Opening of Epoxides02:26

Base-Catalyzed Ring-Opening of Epoxides

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Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
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Metathesis-Sourced Epoxides in Ring-Opening Copolymerization: Selective Access to Degradable Polythioesters.

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Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene
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Sequence Control in Sulphur-Containing Ring-Opening Co- and Terpolymerisations.

Bhargav R Manjunatha1, Cesare Gallizioli1, Christoph Fornacon-Wood1

  • 1Makromolekulare Chemie, Universität Bayreuth, Universitätsstraße 30, 95447, Bayreuth, Germany.

Angewandte Chemie (International Ed. in English)
|May 5, 2025
PubMed
Summary

New methods enable precise synthesis of sulfur-containing polymers, offering enhanced properties like degradability and recyclability. This opens doors for novel materials and applications by controlling sulfur chemistry.

Keywords:
Polymerisation CatalysisRing‐Opening PolymerisationSulphur‐Containing Polymers

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Organic Synthesis

Background:

  • Sulfur-containing polymers offer unique material properties beyond commodity plastics.
  • Current synthesis methods for these polymers are underdeveloped and difficult to control.
  • Sulfur center reshuffling during copolymerization presents a significant synthetic challenge.

Purpose of the Study:

  • To review recent advancements in the selective synthesis of sulfur-containing polymers.
  • To provide a roadmap for accessing tailored sulfur-containing co- and terpolymer structures.
  • To highlight the potential of these polymers in emerging applications.

Main Methods:

  • Review of recent methodologies for controlling sulfur-center reactions in polymerization.
  • Analysis of techniques that suppress or utilize sulfur-center reshuffling.
  • Exploration of ring-opening copolymerization strategies.

Main Results:

  • Emerging methodologies allow precise control over sulfur-containing polymer structures.
  • These polymers demonstrate improved degradability, chemical recyclability, and crystallinity.
  • New monomer feedstocks become accessible through controlled sulfur chemistry.

Conclusions:

  • Precise synthesis of sulfur-containing polymers is now achievable.
  • These advanced polymers offer superior properties compared to oxygen-based analogues.
  • Controlled sulfur chemistry is key to unlocking novel material applications.