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Related Concept Videos

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

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

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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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,...
Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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,...
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 acceptor.
Base-Catalyzed Ring-Opening of Epoxides02:26

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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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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 of a...

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Metal-Dependent Kinetic Control in Cationic-Anionic Synchronous Ring-Opening Polymerization.

Jie Xuan1, Wenli Wang1, Yunqing Zhu1,2

  • 1Department of Polymeric Materials, Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, Tongji University, Shanghai, China.

Angewandte Chemie (International Ed. in English)
|June 18, 2026
PubMed
Summary
This summary is machine-generated.

This study explores how p-block metal chlorides control synchronous polymerization for creating block copolymers. Different metal chlorides enable copolymer formation but significantly alter polymerization rates, acting as kinetic regulators.

Keywords:
2‐oxazolinescyclic esterskineticsp‐block metalsring‐opening polymerization

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Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by π-π Stacking Interactions

Published on: October 10, 2016

Area of Science:

  • Polymer Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Synchronous polymerization combines different reaction pathways for advanced polymer synthesis.
  • Achieving controlled block copolymer synthesis via synchronous polymerization is challenging due to the need to balance opposing reaction mechanisms.
  • Cationic-anionic synchronous ring-opening polymerization (CAP) offers a route to well-defined block copolymers.

Purpose of the Study:

  • To investigate the role of p-block metal chlorides in regulating cationic-anionic synchronous ring-opening polymerization (CAP).
  • To understand how different metal centers influence the kinetics and feasibility of copolymerizing 2-oxazolines and cyclic esters.
  • To establish a strategy for tuning polymer growth rates in multi-mechanistic polymerization systems.

Main Methods:

  • Systematic investigation of various p-block metal chlorides (GaCl3, InCl3, SnCl4, SbCl3, BiCl3).
  • Kinetic analysis of polymerization rates for 2-oxazolines and cyclic esters.
  • Lewis acidity measurements and density functional theory (DFT) calculations.

Main Results:

  • Synchronous copolymerization was broadly accessible across the studied p-block metal chlorides, confirming the robustness of the CAP framework.
  • The rate of 2-oxazoline polymerization was highly sensitive to the metal center identity, while cyclic ester polymerization was less affected.
  • Metal-dependent electronic interactions at the propagating chain end were identified as key modulators of oxazoline activation.

Conclusions:

  • p-Block metal chlorides function primarily as kinetic regulators in synchronous CAP systems.
  • The identity of the metal center allows for decoupling polymerization feasibility from rate control.
  • This work provides a general strategy for precisely tuning polymer growth in complex polymerization processes.