Related Experiment Video
Updated: Jul 2, 2025
08:12
Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
Published on: December 16, 2022
3.3K
Ring-opening-isomerization anionic polymerization via Brook rearrangement
Asuka Hamaguchi1, Masaya Terasaki1, Kaoru Adachi1
1Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan. kadachi@kit.ac.jp.
Chemical Communications (Cambridge, England)
|February 20, 2024
Summary
A novel ring-opening isomerization polymerization technique was developed. This method utilizes a unique epoxy monomer, leading to exclusive anionic polymerization via ring-opening and Brook rearrangement.
Area of Science:
- Polymer Chemistry
- Organic Synthesis
Background:
- Ring-opening polymerization (ROP) is a versatile method for polymer synthesis.
- Brook rearrangement is a silicon-to-carbon or silicon-to-oxygen rearrangement.
Purpose of the Study:
- To develop a novel ring-opening isomerization polymerization (ROIP) method.
- To design and synthesize a specific epoxy monomer for this polymerization.
Main Methods:
- Utilized a combination of epoxide ring-opening and Brook rearrangement.
- Designed an epoxy monomer featuring a benzyltrimethylsilyl group.
- Characterized the resulting polymer using Nuclear Magnetic Resonance (NMR) and Matrix-Assisted Laser Desorption/Ionization-Time of Flight Mass Spectrometry (MALDI-TOF-MS).
Main Results:
- Successfully developed a new ROIP technique.
- The designed epoxy monomer enabled the polymerization process.
- Characterization confirmed exclusive polymerization via a ring-opening-isomerization anionic mechanism.
Conclusions:
- The developed ROIP method is effective for synthesizing polymers.
- The benzyltrimethylsilyl-containing epoxy monomer is suitable for this specific polymerization pathway.
- This study demonstrates a novel approach to anionic polymerization through ring-opening and rearrangement.
More Related Videos
Related Concept Videos
01:16Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
2.6K
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...
2.6K
00:57Cationic Chain-Growth Polymerization: Mechanism
2.3K
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...
2.3K
01:04Anionic Chain-Growth Polymerization: Mechanism
2.0K
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...
2.0K
01:20Anionic Chain-Growth Polymerization: Overview
2.1K
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,...
2.1K
![[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F12422.jpg&w=3840&q=75)
01:21[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
2.7K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
2.7K
01:13Olefin Metathesis Polymerization: Overview
2.1K
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...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.1K