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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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Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
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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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Simple aryl halides do not react with nucleophiles under normal conditions. However, the reaction can proceed under drastic conditions involving high temperatures and high pressure to give the substituted products. For example, chlorobenzene is converted to phenol using aqueous sodium hydroxide at 350 °C under high pressure by the Dow process. The reaction follows an elimination-addition mechanism involving a benzyne intermediate. Here, the chloride ion is...
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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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Constructing N-Containing Poly(p-Phenylene) (PPP) Films Through A Cathodic-Dehalogenation Polymerization Method.

Xiang Wang1, Lei Zhang1, Jinghang Wu1

  • 1Department of Materials Science and Engineering, City University of Hong Kong, Kowloon, Hong Kong SAR, 999077, P. R. China.

Small Methods
|April 15, 2024
PubMed
Summary
This summary is machine-generated.

New nitrogen-containing poly(p-phenylene) (PPP) films were synthesized using an electrochemical method. These novel N-containing PPP films show promising performance for alkaline hydrogen evolution reactions.

Keywords:
N‐containing poly(p‐phenylene) (PPP)cathodic polymerizationelectrochemical dehalogenationelectrochemical hydrogen evolutionfilms

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Electrochemistry

Background:

  • Developing novel N-containing poly(p-phenylene) (PPP) films is crucial for new material properties.
  • Replacing carbon atoms with nitrogen in PPP structures can lead to unique polymer characteristics.

Purpose of the Study:

  • To synthesize N-containing PPP films using an electrochemical-dehalogenation polymerization strategy.
  • To investigate the film-forming capabilities of these polymers on various conductive substrates.
  • To evaluate the performance of the synthesized films in alkaline hydrogen evolution reactions.

Main Methods:

  • Electrochemical-dehalogenation polymerization under constant potentials.
  • Utilized 2,5-diiodopyridine (DIPy) and 2,5-dibromopyrazine (DBPz) as starting materials.
  • In situ film formation on silicon, gold, ITO, and nickel substrates.

Main Results:

  • Successfully synthesized two N-containing PPP films, CityU-23 (polypyridine) and CityU-24 (polypyrazine).
  • Demonstrated in situ film formation on diverse conductive substrates, suitable for device fabrication.
  • Achieved good performance in alkaline hydrogen evolution reaction with CityU-23 and CityU-24, showing specific overpotentials and Tafel slopes.

Conclusions:

  • N-containing PPP films can be effectively synthesized via electrochemical polymerization.
  • The synthesized polymers exhibit excellent film-forming properties on various conductive surfaces.
  • These novel N-containing PPP films demonstrate significant potential for applications in hydrogen evolution reactions.