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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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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

Anionic Chain-Growth Polymerization: Mechanism

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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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Olefin Metathesis Polymerization: Overview01:13

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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.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

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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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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes
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Electrochemically switchable polymerization from surface-anchored molecular catalysts.

Miao Qi1, Haochuan Zhang1, Qi Dong1

  • 1Department of Chemistry, Boston College 2609 Beacon St., Chestnut Hill MA 02467 USA dwang@bc.edu jeffery.byers@bc.edu.

Chemical Science
|July 19, 2021
PubMed
Summary
This summary is machine-generated.

Researchers developed solid-state redox-switchable polymerization using iron catalysts on TiO2 nanoparticles. This method creates patterned polymer brushes with tunable properties, enabling advanced surface functionalization.

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Nanotechnology

Background:

  • Redox-switchable polymerization offers control over polymer properties.
  • Extending these reactions to the solid state is crucial for practical applications.
  • Catalyst immobilization on nanoparticles can enhance reactivity and stability.

Purpose of the Study:

  • To achieve solid-state redox-switchable polymerization of lactide and epoxides.
  • To create patterned polymer brushes with spatially controlled chemical composition.
  • To demonstrate an electrically addressable method for surface functionalization.

Main Methods:

  • Anchoring an iron-based catalyst to TiO2 nanoparticles for solid-state polymerization.
  • Utilizing redox-switching of the iron complex to control polymerization.
  • Depositing functionalized nanoparticles on conductive substrates (fluorine-doped tin oxide) for electrical addressing.
  • Employing patterned substrates to achieve spatial control over polymer brush growth.

Main Results:

  • Solid-state redox-switchable polymerization of lactide and epoxides was successfully demonstrated.
  • Polymer brush composition was controlled by the catalyst's oxidation state.
  • Electrically addressable surfaces allowed for spatial control of polymerization.
  • Patterned surfaces with distinct polymer brushes were created, showing tunable physical properties.

Conclusions:

  • Immobilized iron catalysts on TiO2 nanoparticles enable solid-state redox-switchable polymerization.
  • This approach provides precise spatial and chemical control over polymer brush formation.
  • The method holds promise for creating complex, patterned surfaces with tailored functionalities.