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Cationic Chain-Growth Polymerization: Mechanism00:57

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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...
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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...
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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,...
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Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by &#960;-&#960; Stacking Interactions
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Film Confinement Induced "Jump-Percolation" Wetting Transition in Amphiphilic Block Copolymer Films.

Namrata Salunke1, Asritha Nallapaneni1, Guangcui Yuan1,2

  • 1Department of Polymer Engineering, The University of Akron , 250 South Forge Street, Akron, Ohio 44325-0301, United States.

ACS Applied Materials & Interfaces
|September 20, 2017
PubMed
Summary

Amphiphilic triblock copolymer films show a sharp transition from hydrophobic to hydrophilic surface wettability. This change depends on film thickness and morphology, impacting water contact angles significantly.

Keywords:
confinement effectshydrophilicityhydrophobicityjump percolation

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Area of Science:

  • Materials Science
  • Surface Chemistry
  • Polymer Science

Background:

  • Surface wettability is crucial for material applications.
  • Controlling wettability in thin films is challenging.
  • Amphiphilic copolymers offer tunable surface properties.

Purpose of the Study:

  • To investigate the surface wettability transition in amphiphilic triblock copolymer films.
  • To correlate film morphology with wettability changes.
  • To understand the mechanism behind the abrupt wettability transition.

Main Methods:

  • Fabrication of cast films of poly(FOSM)-poly(DMA) triblock copolymer with varying thicknesses.
  • Dynamic water contact angle measurements to assess wettability.
  • Analysis of surface morphology and its relation to film thickness.
  • Optical diffuse reflectance measurements.

Main Results:

  • A sharp, first-order-like wettability transition from hydrophobic to hydrophilic was observed for films with thickness between 200-300 nm.
  • An abrupt change in water contact angle from ~116° to ~40° occurred after an induction time, with an ultrafast decay rate.
  • This transition is attributed to a 'jump percolation' wetting mechanism driven by the density of poly(DMA) wetting domains.
  • Outside the transition range, wettability gradually changed with film thickness, showing a monotonic increase in poly(DMA) domain coverage.
  • Diffuse reflectance properties correlated with the transition morphology.

Conclusions:

  • Film thickness critically controls surface wettability in these amphiphilic triblock copolymers.
  • The observed abrupt wettability transition is governed by a percolation phenomenon of wetting domains.
  • The findings provide insights into designing surfaces with switchable wettability for advanced applications.