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Related Concept Videos

Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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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...
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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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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...
2.8K
Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

2.4K
Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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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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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Observing polymerization in 2D dynamic covalent polymers.

Gaolei Zhan1,2, Zhen-Feng Cai3,4, Karol Strutyński5

  • 1Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Leuven, Belgium.

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|March 31, 2022
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Summary

This study reveals the real-time polymerization and crystallization dynamics of 2D dynamic covalent polymers using in situ scanning tunnelling microscopy. It quantifies key crystallization parameters and demonstrates abnormal grain growth for single-crystal formation.

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Surface Science

Background:

  • Crystalline 2D polymer quality depends on polymerization and crystallization mechanisms.
  • Understanding these processes is key for tailored material properties in catalysis and optoelectronics.

Purpose of the Study:

  • To characterize the nucleation-elongation processes of a model 2D dynamic covalent polymer.
  • To unveil polymerization and crystallization mechanisms at the (sub)molecular level in real time.
  • To determine essential crystallization parameters and explore crystal growth phenomena.

Main Methods:

  • In situ scanning tunnelling microscopy (STM) for real-time observation.
  • Sequential data analysis of polymerization and crystallization.
  • Atomistic computer modeling for rationalization.

Main Results:

  • Observed amorphous-to-crystalline transition and time-dependent nucleus evolution.
  • Identified 'non-classical' crystallization pathways.
  • Experimentally determined critical nucleus size, nucleation rate, and growth rate.
  • Demonstrated abnormal grain growth influencing 2D crystal formation.

Conclusions:

  • Provided a detailed picture of dynamic on-surface polymerization.
  • Established a method for accurate determination of crystallization parameters.
  • Showed that abnormal grain growth can be utilized to achieve single-crystal 2D polymers.