Related Experiment Video
Updated: Sep 20, 2026

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
Published on: June 20, 2019
A theoretical study on the mechanism of the cyclopolymerization of diallyl monomers
N S Tuzun1, V Aviyente, K N Houk
1Chemistry Department, Bogazici University, 34342, Bebek, Istanbul, Turkey.
Abstract:
The cyclization and intermolecular propagation steps of the cyclopolymerization mechanism are studied with density functional theory. In addition to standard cyclization and intermolecular propagation reactions of cyclopolymerization, competing reactions that lead to chain transfer and termination are also discussed. The mechanistic study of the cyclopolymerization reaction of two representative monomers, N,N-diallylamine (1) and N,N-dimethyl-N,N-diallylamonium (2), was carried out with B3LYP/6-31G computations. Monomer 1 has almost the same activation barriers for homopolymerization and cyclization. In monomer 2, cyclization is much more facile than homopolymerization, leading to the higher cyclopolymerization efficiency. In the case of 2, methyl substituents on nitrogen inhibit hydrogen abstraction, whereas in 1, hydrogen abstraction reactions from the neutral monomer yield stabilized products leading to chain transfer. Calculations show that facile competing reactions of monomer 1 lower the polymerization efficiency. Monomer 2 displays a stronger preference for cyclization relative to other processes.
Related Concept Videos
Cationic Chain-Growth Polymerization: Mechanism
Anionic Chain-Growth Polymerization: Mechanism
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Free-Radical Chain Reaction and Polymerization of Alkenes
Cycloaddition Reactions: Overview

