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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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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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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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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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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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Photo-Triggerable Polymerization and Depolymerization of Stiff-Stilbene Lactones.

Yong-Liang Su1, Wei Xiong1, Timothy M Hunter1

  • 1School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.

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Summary
This summary is machine-generated.

This study presents photoswitchable cyclic monomers that enable controlled polymerization and depolymerization using light. This innovation offers a new pathway for creating adaptable and sustainable polymer materials.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Photochemistry

Background:

  • Photoswitchable polymers offer external stimuli control over polymerization.
  • Controlling polymerization and depolymerization is key for advanced material design.

Purpose of the Study:

  • To develop a photoswitchable ring-opening polymerization (ROP) system using stiff-stilbene cyclic monomers.
  • To investigate the impact of E/Z photoisomerization on monomer ring strain and polymerization dynamics.
  • To create sustainable polymers with tunable thermal, optical, and responsive properties.

Main Methods:

  • Synthesis of stiff-stilbene lactones with varying linker lengths.
  • Evaluation of polymerization and depolymerization behavior under light stimuli.
  • Density Functional Theory (DFT) calculations to understand photoisomerization effects.

Main Results:

  • Successful synthesis of photoswitchable stiff-stilbene lactones.
  • Demonstration of light-controlled polymerization and depolymerization.
  • Polymers exhibited tunable thermal and optical properties, including liquid crystallinity.
  • DFT calculations confirmed the role of E/Z photoisomerization in controlling ROP.

Conclusions:

  • A novel photoswitchable ROP system based on stiff-stilbene monomers was established.
  • This system allows for dynamic control over polymer properties and recovery of monomers.
  • The findings pave the way for designing adaptive and sustainable polymer materials.