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Related Concept Videos

Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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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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Radical Chain-Growth Polymerization: Mechanism01:09

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
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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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Radical Chain-Growth Polymerization: Chain Branching01:17

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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

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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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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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Preparation of DNA-crosslinked Polyacrylamide Hydrogels
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How chain dynamics affects crack initiation in double-network gels.

Yong Zheng1,2, Takahiro Matsuda3, Tasuku Nakajima4,3

  • 1Graduate School of Life Science, Hokkaido University, Sapporo 001-0021, Japan.

Proceedings of the National Academy of Sciences of the United States of America
|December 1, 2021
PubMed
Summary

Solvent viscosity impacts double-network gels

Keywords:
chain dynamicscrack initiationdouble-network gelsnonlinear crack tip analysis

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Area of Science:

  • Materials Science
  • Polymer Science
  • Soft Matter Physics

Background:

  • Double-network gels are tough soft materials with two distinct elastic networks.
  • Their high crack resistance stems from a large damage zone formed by brittle network rupture.
  • Understanding the factors governing this damage zone is key to their fracture mechanics.

Purpose of the Study:

  • To investigate the influence of solvent viscosity on the fracture mechanics of double-network gels.
  • To elucidate the role of polymer dynamics in crack initiation and propagation.
  • To propose a mechanism explaining the observed effects of solvent viscosity.

Main Methods:

  • Experimental investigation of double-network gel fracture under varying solvent viscosities.
  • Analysis of crack propagation, damage zone formation, and material deformation.
  • Development of a theoretical model incorporating polymer dynamics.

Main Results:

  • Increased solvent viscosity significantly reduces the necking zone size at crack initiation.
  • Fracture toughness of the gels decreases with increasing solvent viscosity.
  • Tensile behavior of the gels remains unaffected by solvent viscosity changes.

Conclusions:

  • Polymer dynamics of the stretchable network, triggered by brittle network rupture, critically influences fracture toughness.
  • A delayed blunting mechanism, considering polymer dynamics, explains the solvent viscosity effect on crack initiation.
  • This study reveals a crucial missing element in the fracture mechanism of double-network gels.