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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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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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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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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.
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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.
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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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Dynamic Heterogeneity in Ring-Linear Polymer Blends.

Anna F Katsarou1, Alexandros J Tsamopoulos2, Dimitrios G Tsalikis3

  • 1Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, UK.

Polymers
|April 3, 2020
PubMed
Summary
This summary is machine-generated.

Molecular dynamics simulations reveal that ring molecule relaxation times in blends with linear chains are broadly distributed. Threading by linear chains significantly slows down ring dynamics, creating dynamic heterogeneity.

Keywords:
dynamic heterogeneityringsthreading events

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Area of Science:

  • Polymer Physics
  • Materials Science
  • Computational Chemistry

Background:

  • Understanding polymer dynamics is crucial for material properties.
  • Ring polymers exhibit unique relaxation behaviors compared to linear chains.
  • Blending polymers can alter their dynamic properties.

Purpose of the Study:

  • To investigate the orientational relaxation of ring molecules in blends with linear chains using molecular dynamics.
  • To quantify the impact of threading on ring polymer dynamics.
  • To elucidate the mechanisms controlling relaxation in these complex systems.

Main Methods:

  • Direct statistical analysis of long molecular dynamics (MD) trajectories.
  • Analysis of orientational relaxation times for individual ring molecules.
  • Deconvolution of relaxation data into exponential functions to identify contributing mechanisms.

Main Results:

  • A very broad distribution of ring relaxation times was observed, widening with increased molecular length and linear chain concentration.
  • Dynamic heterogeneity was more pronounced in blends than in pure ring melts.
  • Threading events between ring and linear chains were identified as the primary cause for the increased relaxation times and dynamic heterogeneity.
  • Unthreaded/singly-threaded rings relaxed similarly to pure melts, while multiply-threaded rings relaxed significantly slower.

Conclusions:

  • The relaxation dynamics of ring molecules in blends are predominantly controlled by their topological state (threading) with linear chains.
  • Multiply-threaded rings experience significantly longer relaxation times due to persistent topological interactions.
  • The study quantifies the distinct relaxation mechanisms and their contributions in both pure ring melts and blends.