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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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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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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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For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
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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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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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Trefoil Knot Hydrodynamic Delocalization on Sheared Ring Polymers.

Maximilian Liebetreu1, Marisol Ripoll2, Christos N Likos1

  • 1Faculty of Physics, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria.

ACS Macro Letters
|May 27, 2022
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Summary
This summary is machine-generated.

Ring polymers exhibit unique behavior under shear flow, resisting shortening due to solvent interactions. Their rotation shifts from tank-treading to tumbling, impacting polymer dynamics and rheology.

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Area of Science:

  • Polymer Physics
  • Rheology
  • Computational Soft Matter

Background:

  • Ring polymers, unlike linear ones, possess a unique topology.
  • Understanding polymer behavior under flow is crucial for materials science.

Purpose of the Study:

  • To investigate the behavior of unknotted and trefoil-knotted ring polymers under shear flow.
  • To elucidate the role of hydrodynamic interactions and polymer topology on conformational dynamics.

Main Methods:

  • Mesoscopic simulations were employed to model polymer behavior.
  • Analysis focused on conformational changes, extension, and rotational dynamics.

Main Results:

  • Ring polymers do not shorten in the vorticity direction at high shear rates, contrary to linear polymers.
  • Hydrodynamic interactions induce backflow, favoring contour fluctuations and tumbling rotations over tank-treading.
  • Trefoil knots become extended and delocalized.

Conclusions:

  • Shear flow significantly alters ring polymer dynamics, driven by hydrodynamic interactions.
  • These findings are critical for understanding the rheological properties of concentrated ring polymer solutions.
  • The study provides insights into complex polymer systems with varying topologies.