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Related Concept Videos

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: 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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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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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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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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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Transient Covalent Polymers through Carbodiimide-Driven Assembly.

Nirob K Saha1, William S Salvia1, Dominik Konkolewicz1

  • 1Department of Chemistry and Biochemistry, Miami University, 651 E High St, Oxford, OH, 45056, United States.

Angewandte Chemie (International Ed. in English)
|May 21, 2024
PubMed
Summary
This summary is machine-generated.

Researchers created novel transient covalent polymers from dicarboxylic acids using EDC. These polymers offer tunable lifetimes and controlled assembly/disassembly, advancing nonequilibrium polymerization systems.

Keywords:
anhydridescarbodiimideschemical fuelsnonequilibrium assemblypolymerization

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Area of Science:

  • Polymer Chemistry
  • Supramolecular Chemistry
  • Materials Science

Background:

  • Biochemical systems utilize out-of-equilibrium polymers under kinetic control.
  • Abiotic supramolecular polymers driven by chemical fuels are well-studied.
  • Polymers with transient covalent bonds are underexplored but offer potential for stronger transient structures and tunable kinetics.

Purpose of the Study:

  • To investigate the formation and properties of transient covalent polymers derived from simple aqueous dicarboxylic acids.
  • To explore the potential of these polymers in nonequilibrium polymerization systems.
  • To demonstrate control over polymer assembly and disassembly kinetics.

Main Methods:

  • Polymerization of aqueous dicarboxylic acids using the carbodiimide EDC.
  • Characterization of polymer molecular weights and decomposition kinetics.
  • Systematic investigation of factors influencing polymer properties (solvent polarity, reagent concentrations, temperature, monomer structure).

Main Results:

  • Successfully generated transient covalent poly(anhydrides) with molecular weights over 15,000.
  • Demonstrated polymer decomposition over hours to weeks, with tunable disassembly kinetics.
  • Identified significant control over assembly and disassembly kinetics through monomer design and reaction conditions.

Conclusions:

  • Simple aqueous dicarboxylic acids and EDC can form transient covalent poly(anhydrides).
  • These polymers exhibit controllable lifetimes and kinetics, complementing existing supramolecular systems.
  • The findings highlight the potential for fine-tuned kinetic control in nonequilibrium polymerization.