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Related Concept Videos

Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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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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Cationic Chain-Growth Polymerization: Mechanism00:57

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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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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Step-Growth Polymerization: Overview01:03

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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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Anionic Chain-Growth Polymerization: Mechanism01:04

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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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Thermally bisignate supramolecular polymerization.

Kotagiri Venkata Rao1,2, Daigo Miyajima1, Atsuko Nihonyanagi1

  • 1RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.

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|October 25, 2017
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Summary
This summary is machine-generated.

This study introduces a novel supramolecular polymerization that occurs upon both heating and cooling. This unique thermoresponsive behavior is achieved using a specialized metalloporphyrin monomer and a scavenger molecule.

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Area of Science:

  • Supramolecular Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Supramolecular polymers exhibit thermodynamic reversibility, making them suitable for stimuli-responsive applications.
  • Typically, supramolecular polymers disassemble upon heating, limiting their thermal responsiveness.
  • Developing polymers with complex thermal responses is crucial for advanced material applications.

Purpose of the Study:

  • To report a novel supramolecular polymerization that occurs upon both heating and cooling.
  • To investigate the mechanism behind this unusual thermally bisignate behavior.
  • To explore the potential for creating advanced thermoresponsive supramolecular materials.

Main Methods:

  • Synthesis of a tailored metalloporphyrin monomer with eight amide-containing side chains.
  • Utilizing a scavenger molecule (1-hexanol) in a dodecane-based solvent.
  • Investigating polymerization behavior through controlled heating and cooling cycles around 50°C.

Main Results:

  • A highly thermostable one-dimensional supramolecular polymer is formed via π-stacking and multivalent hydrogen bonding.
  • A scavenger molecule competitively binds to the monomer at ~50°C, inhibiting polymerization.
  • Both cooling and heating unlock the monomer for polymerization by altering scavenger-monomer interactions.

Conclusions:

  • A novel supramolecular polymerization exhibiting heating-induced and cooling-induced assembly has been demonstrated.
  • The observed thermally bisignate behavior is attributed to scavenger-mediated monomer unlocking.
  • This phenomenon offers a pathway to supramolecular polymers with complex and tunable thermoresponsive properties, analogous to critical solution temperature phenomena.