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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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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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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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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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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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Dynamic covalent polymers enabled by reversible isocyanate chemistry.

Wenxing Liu1, Shijia Yang2, Lei Huang1

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Responsive materials utilizing dynamic covalent bonds (DCBs) are engineered using reversible isocyanate chemistry. This approach enables thermally adaptable polymers for applications like self-healing and recycling.

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Area of Science:

  • Polymer Science
  • Materials Chemistry
  • Organic Chemistry

Background:

  • Dynamic covalent bonds (DCBs) enable responsive materials through reversible association and dissociation.
  • Isocyanate-based bonds (IBs), including urethane, thiourethane, and urea, offer reversible chemistry upon heating.

Purpose of the Study:

  • To overview mechanisms and experimental factors influencing dynamic isocyanate-based bonds.
  • To discuss construction strategies for dynamic covalent polymers using isocyanate chemistry.
  • To outline applications of these dynamic polymers.

Main Methods:

  • Review of reversible isocyanate chemistry mechanisms.
  • Analysis of factors affecting dynamic bond features.
  • Discussion of polymer construction strategies and applications.

Main Results:

  • Isocyanate-based bonds exhibit reversible dissociation into starting chemicals upon heating.
  • Successful construction strategies for dynamic polyurethanes, polyureas, and polythiourethanes are detailed.
  • Key applications in recycling, self-healing, shape morphing, 3D printing, and composites are highlighted.

Conclusions:

  • Reversible isocyanate chemistry provides a robust platform for designing thermally adaptable materials.
  • Dynamic covalent polymers based on isocyanates offer significant potential for advanced material applications.