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Related Concept Videos

Polymers: Molecular Weight Distribution01:10

Polymers: Molecular Weight Distribution

For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
Polymer Classification: Crystallinity01:21

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...
Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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

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: Mechanism00:57

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,...

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Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst
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Polyferrocenylsilane Block Copolymer Spherulites in Dilute Solution.

Jingjie Jiang1, Ehsan Nikbin2, Garion Hicks1

  • 1Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada.

Journal of the American Chemical Society
|January 4, 2023
PubMed
Summary

Researchers developed a one-pot method to create uniform 3D spherulite structures from poly(ferrocenyldimethylsilane) block copolymers (BCP). This breakthrough identifies key requirements for fabricating these complex structures in solution.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Self-assembly of block copolymers (BCP) into uniform 3D structures in solution is rare.
  • General prerequisites for fabricating specific 3D structures are largely unknown.

Purpose of the Study:

  • To establish a general protocol for fabricating uniform 3D spherulite-like structures and their precursors from poly(ferrocenyldimethylsilane) (PFS) BCPs.
  • To identify the general prerequisites for the formation of these structures.

Main Methods:

  • A simple one-pot direct self-assembly protocol involving heating and cooling of PFS BCPs in various solvents.
  • Investigation of structure evolution with increasing annealing temperature and supersaturation degree.
  • Identification of critical block ratios and secondary crystal formation for spherulite fabrication.

Main Results:

  • Uniform spherulite-like structures and their precursors were successfully prepared from various PFS BCPs in diverse solvents.
  • Structure evolution from lamellae to spherulites was observed with increasing temperature and supersaturation.
  • Key prerequisites identified: corona/PFS core block ratios of 1-5.5 and early secondary crystal development.

Conclusions:

  • A general one-pot direct self-assembly protocol for PFS BCP spherulites and precursors has been established.
  • The study provides general concepts for fabricating and optimizing semicrystalline BCP spherulites.
  • These findings hold promise for applications in optics, electronics, and biomedicine.