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Related Concept Videos

Polymers02:34

Polymers

35.7K
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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Polymer Classification: Architecture01:14

Polymer Classification: Architecture

2.7K
Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.3K
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...
2.3K
Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

3.4K
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.
Many natural and synthetic polymers are produced by...
3.4K
Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

2.1K
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,...
2.1K
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...
2.0K

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Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene
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Reprocessable Polymer Networks Containing Sulfur-Based, Percolated Dynamic Covalent Cross-Links and Percolated or

Logan M Fenimore1, Mohammed A Bin Rusayyis2, Claire C Onsager3

  • 1Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL, 60208, USA.

Macromolecular Rapid Communications
|July 11, 2024
PubMed
Summary

This study introduces covalent adaptable networks (CANs) reinforced with static cross-links, maintaining recyclability. These networks exhibit tunable stress relaxation behaviors influenced by cross-link content and polymer backbone dynamics.

Keywords:
covalent adaptable networkcross‐linkdynamicpermanentsustainabilityvitrimer

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Area of Science:

  • Polymer Chemistry
  • Materials Science

Background:

  • Covalent adaptable networks (CANs) offer dynamic properties but often lack robustness.
  • Incorporating permanent cross-links can enhance network stability without compromising recyclability.

Purpose of the Study:

  • To synthesize and characterize poly(n-hexyl methacrylate) (PHMA) and poly(n-lauryl methacrylate) (PLMA) based CANs with both static and dynamic cross-links.
  • To investigate the impact of static cross-link content on the mechanical properties, particularly stress relaxation, of these CANs.
  • To elucidate the relationship between network architecture, polymer mobility, and stress relaxation mechanisms.

Main Methods:

  • Synthesis of PHMA and PLMA networks using bis(2-methacryloyl)oxyethyl disulfide (DSDMA) as static cross-linker and BiTEMPS methacrylate as dynamic cross-linker.
  • Evaluation of network robustness and recyclability, including cross-link density recovery.
  • Analysis of stress relaxation responses under varying static cross-link concentrations.
  • Determination of activation energies for stress relaxation to understand underlying mechanisms.

Main Results:

  • Successfully synthesized robust and recyclable CANs with tunable static cross-link content.
  • Demonstrated full recovery of cross-link density after recycling, confirming network integrity.
  • Observed distinct stress relaxation behaviors in dissociative CANs versus those with percolated static cross-links.
  • Identified that BiTEMPS methacrylate dissociation dominates relaxation in non-percolated networks, while side-chain segmental relaxation (beta relaxation) governs relaxation in percolated networks.

Conclusions:

  • The developed CANs offer a promising approach to create materials with both enhanced mechanical properties and recyclability.
  • The interplay between static cross-links and dynamic covalent bonds allows for precise control over material response.
  • Understanding the dominant relaxation mechanisms (cross-link dissociation vs. segmental motion) is crucial for designing advanced adaptable materials.