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Related Concept Videos

Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
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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.
Many natural and synthetic polymers are produced by...
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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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Anionic Chain-Growth Polymerization: Overview01:20

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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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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 species into...
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Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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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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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Driven anomalous diffusion: An example from polymer stretching.

Takuya Saito1, Takahiro Sakaue2

  • 1Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan.

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics
|August 15, 2015
PubMed
Summary
This summary is machine-generated.

Tension propagation in polymers exhibits anomalous dynamics under strong force regimes. Molecular dynamics simulations reveal nonlinear memory kernels and complex fluctuation relations during polymer stretching.

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Area of Science:

  • Polymer physics
  • Statistical mechanics
  • Soft matter science

Background:

  • Tension propagation governs dynamics in macromolecular systems.
  • Two regimes exist: weak and strong force.
  • Understanding these regimes is crucial for polymer behavior.

Purpose of the Study:

  • Investigate dynamical fluctuations in long polymers during stretching.
  • Characterize the anomalous response in the strong force regime.
  • Elucidate the role of stress hardening in polymer dynamics.

Main Methods:

  • Theoretical analysis using the generalized Langevin equation.
  • Focus on the strong force regime of tension propagation.
  • Molecular dynamics simulations to validate theoretical predictions.

Main Results:

  • Anomalous average drift response observed in polymer stretching.
  • A nonlinear memory kernel characterizes the polymer's response.
  • A nontrivial relationship exists between response and fluctuations.
  • Stress hardening's impact on spring constant is identified.

Conclusions:

  • The generalized Langevin equation effectively describes polymer stretching dynamics.
  • Nonlinear memory kernels and fluctuation relations are key features.
  • Molecular dynamics simulations confirm the theoretical framework.