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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
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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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For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
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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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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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A Crystalline 1D Dynamic Covalent Polymer.

Elisabet De Bolòs1, Marta Martínez-Abadía1, Félix Hernández-Culebras1

  • 1POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72, Donostia-San Sebastián 20018, Spain.

Journal of the American Chemical Society
|August 22, 2022
PubMed
Summary
This summary is machine-generated.

Researchers synthesized a crystalline one-dimensional polymer using dynamic covalent chemistry. This breakthrough enables better understanding of polymer properties and creates materials with enhanced charge transport capabilities.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Solid-State Physics

Background:

  • Crystalline one-dimensional polymers are crucial for understanding structure-property relationships in materials.
  • Achieving crystalline one-dimensional polymers is challenging due to the tendency for amorphous or semi-crystalline phases.
  • These materials offer potential for enhanced thermal, mechanical, and conducting properties.

Purpose of the Study:

  • To report the synthesis of a crystalline one-dimensional polymer in solution.
  • To investigate the structure-property relationship, particularly charge transport.
  • To demonstrate a method for creating ordered polymeric materials.

Main Methods:

  • Dynamic covalent chemistry for polymer synthesis.
  • Microcrystal electron diffraction for structural confirmation.
  • Charge transport studies and theoretical calculations.

Main Results:

  • Successfully synthesized a crystalline one-dimensional polymer in solution.
  • Unambiguously confirmed the polymer's structure using microcrystal electron diffraction.
  • Demonstrated that π-stacked chains create optimal channels for charge transport.

Conclusions:

  • The synthesis of crystalline one-dimensional polymers is achievable via dynamic covalent chemistry.
  • The π-stacked structure is key to the polymer's excellent charge transport properties.
  • This work advances the development of advanced polymeric materials with tailored electronic properties.