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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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Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

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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.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

2.0K
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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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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Radical Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

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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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Microfluidic Preparation of Liquid Crystalline Elastomer Actuators
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Enhancing Mechanophore Activation through Polymer Crystallization.

Qinxin Sheng1, Rui Tan1, Xiaohua Zhang2

  • 1State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.

ACS Macro Letters
|November 21, 2024
PubMed
Summary
This summary is machine-generated.

Polymer crystallization significantly boosts mechanophore activation. This study shows crystallization-induced forces are more effective than external forces, especially for low molecular weight polymers, enhancing polymer mechanochemistry.

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Area of Science:

  • Polymer Science
  • Mechanochemistry
  • Materials Science

Background:

  • Mechanophore activation in bulk polymers often suffers from low rates.
  • Understanding factors influencing mechanochemical reactions is crucial for developing new materials and applications.

Purpose of the Study:

  • To investigate the effect of polymer crystallization on mechanophore activation.
  • To compare the efficacy of crystallization-induced forces versus external mechanical forces (compression, ultrasonication) in activating mechanophores.
  • To elucidate the relationship between polymer properties (molecular weight, crystallinity, chirality) and mechanophore activation.

Main Methods:

  • Utilized rhodamine-containing poly(lactic acid) (PLA) and polycaprolactone (PCL) as model systems.
  • Investigated mechanophore activation under polymer crystallization conditions.
  • Applied macroscopic mechanical forces (compression, ultrasonication) for comparative analysis.
  • Correlated mechanophore activation with polymer degree of crystallinity and molecular weight.

Main Results:

  • Polymer crystallization was found to significantly enhance mechanophore activation rates.
  • Micromechanical forces generated during crystallization proved more effective than macroscopic forces.
  • This enhancement was particularly evident in polymers with lower molecular weights.
  • Mechanophore activation showed a positive correlation with both polymer crystallinity and molecular weight.
  • Polymer chirality did not impact the observed mechanophore activation.

Conclusions:

  • Polymer crystallization is a potent strategy for enhancing mechanophore activation in bulk polymers.
  • Crystallization-induced forces offer a novel and effective method for driving mechanochemical reactions.
  • The findings provide valuable insights for designing advanced mechanochemically active polymers and materials.