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Anionic Chain-Growth Polymerization: Mechanism

Anionic Chain-Growth Polymerization: Mechanism

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.

Cationic Chain-Growth Polymerization: Mechanism

Cationic Chain-Growth Polymerization: Mechanism

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,...

Step-Growth Polymerization: Overview

Step-Growth Polymerization: Overview

Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...

Anionic Chain-Growth Polymerization: Overview

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,...

Polymer Classification: Crystallinity

Polymer Classification: Crystallinity

Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...

Radical Chain-Growth Polymerization: Mechanism

Radical Chain-Growth Polymerization: Mechanism

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 species into the...

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Related Experiment Video

Updated: May 10, 2026

Methods for the Self-integration of Megamolecular Biopolymers on the Drying Air-LC Interface

Methods for the Self-integration of Megamolecular Biopolymers on the Drying Air-LC Interface

Published on: April 7, 2017

Anomalous drying dynamics of a polymer solution on a substrate.

Shunto Arai¹, Masao Doi

¹Graduate School of Engineering, The University of Tokyo, 113-8656, Tokyo, Japan. arai1010@iis.u-tokyo.ac.jp

The European Physical Journal. E, Soft Matter

|June 26, 2013

Summary

Solvent evaporation from polymer solutions can increase internal pressure, contrary to previous assumptions. This pressure pushes liquid out from below the surface skin layer, driven by skin layer structural changes.

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Methods for the Self-integration of Megamolecular Biopolymers on the Drying Air-LC Interface

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Published on: April 7, 2017

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Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Published on: January 17, 2018

Area of Science:

Polymer Science
Materials Science
Physical Chemistry

Background:

Formation of a surface elastic layer (skin) is common during volatile solvent evaporation from polymer solutions.
Previously, solvent evaporation was thought to decrease internal solution pressure after skin formation.

Purpose of the Study:

To investigate the pressure dynamics within a polymer solution during solvent evaporation after skin formation.
To challenge the conventional understanding of pressure changes in such systems.

Main Methods:

Observation of a poly(methyl methacrylate) (PMMA) in acetone droplet on a substrate.
Monitoring liquid behavior and pressure changes during solvent evaporation.

Main Results:

The liquid below the skin layer was observed to be expelled as solvent evaporation continued.
These observations indicate an increase in internal solution pressure during solvent evaporation.

Conclusions:

Solvent evaporation in PMMA/acetone systems leads to increased internal pressure, not decreased pressure.
Shrinkage and structural alterations within the formed skin layer are the likely cause of this pressure increase.