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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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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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Anionic Chain-Growth Polymerization: Overview01:20

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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 Chain-Growth Polymerization: Mechanism01:04

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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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Radical Chain-Growth Polymerization: Mechanism01:09

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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...
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Radical Chain-Growth Polymerization: Chain Branching01:17

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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
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Azobenzene-Containing Liquid Crystalline Twisted Ribbons via Polymerization-Induced Hierarchical Self-Assembly.

Zichao Deng1, Yalan Sun1, Song Guan1

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|August 3, 2023
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Summary

Researchers developed a new method for creating twisted polymer ribbons using polymerization-induced hierarchical self-assembly (PIHSA) with poor control. This method allows for better regulation of liquid crystalline polymer particle morphologies.

Keywords:
RAFT agent end groupsazobenzeneliquid crystallizationpolymerization-induced self-assemblytwisted ribbons

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Polymerization-induced hierarchical self-assembly (PIHSA) is a key method for creating anisotropic polymeric particles.
  • Controlling the morphology of liquid crystalline (LC) polymer assemblies remains a challenge.
  • Azobenzene-containing polymers offer unique self-assembly properties.

Purpose of the Study:

  • To explore new methods for regulating the morphologies of liquid crystalline polymer assemblies.
  • To investigate the fabrication of twisted ribbons via PIHSA.
  • To understand the mechanism behind the formation of twisted ribbons.

Main Methods:

  • Utilizing a poorly controlled reversible addition-fragmentation chain transfer (RAFT) polymerization.
  • Employing a specific RAFT agent: cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid-2-(2-pyridyldithio) ethyl ester.
  • Observing morphological evolution in the PIHSA system.

Main Results:

  • Successfully fabricated twisted ribbons through poorly controlled PIHSA.
  • Identified broad molecular weight distribution as a decisive factor in ribbon twisting.
  • Observed a correlation between supramolecular chirality, symmetry breaking, and ribbon twist.

Conclusions:

  • This study presents a novel route to control LC polymer particle morphologies.
  • The findings enrich the understanding of PIHSA mechanisms.
  • The method provides insights into supramolecular chirality induction in polymer assemblies.