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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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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
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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.
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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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An Oriented Polymer in a Dynamic Microsolution Pierces Molecular Rings: An Approach toward Polyrotaxane Synthesis

Munenori Numata1, Kaori Tanaka1, Atsushi Asai1

  • 1Department of Biomolecular Chemistry, Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, Shimogamo, Sakyo-ku, Kyoto 606-8522, Japan.

Journal of the American Chemical Society
|May 13, 2025
PubMed
Summary
This summary is machine-generated.

Dynamic host-guest chemistry was achieved using polymer-ring systems and Hagen-Poiseuille flow. This method creates long pseudodouble-stranded polyrotaxane nanofibers and novel crystalline fibers, overcoming traditional host-guest limitations.

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Area of Science:

  • Supramolecular Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Host-guest chemistry traditionally relies on thermodynamic equilibrium.
  • Dynamic conditions offer new possibilities for molecular assembly.
  • Polymer-ring systems provide a model for studying complex interactions.

Purpose of the Study:

  • To demonstrate host-guest chemistry under dynamic flow conditions.
  • To investigate the formation of pseudodouble-stranded polyrotaxane (DS-PR) nanofibers.
  • To explore a novel active-threading mechanism driven by microfluidics.

Main Methods:

  • Utilized a polymer-ring model with poly(ethylene glycol) (PEG) and γ-cyclodextrin (γ-CD).
  • Applied Hagen-Poiseuille flow to drive guest polymer threading into ring hosts.
  • Systematically varied hydrodynamic and structural parameters to study interactions.

Main Results:

  • Repeated threading of PEG into γ-CD cavities via flow, forming long DS-PR nanofibers.
  • Hierarchical assembly of DS-PR into micrometer-scale crystalline fibers through hydrogen bonding.
  • Observed preferential piercing of γ-CD's wider rim by the PEG chain end, enabling an active-threading mechanism.

Conclusions:

  • Dynamic flow conditions enable efficient host-guest complexation distinct from equilibrium processes.
  • The active-threading mechanism, facilitated by microflow, allows for controlled polymer threading.
  • Demonstrated cothreading of different cyclodextrin types (α-CD and γ-CD) onto a single polymer chain, challenging the lock-and-key paradigm.