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Polymers: Molecular Weight Distribution01:10

Polymers: Molecular Weight Distribution

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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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Polymers: Defining Molecular Weight01:01

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Unlike small molecules with definite molecular weights, polymers are a mixture of individual polymer chains of varying lengths, each with a unique molecular weight.  So, the molecular weight of a polymer is expressed as an average value based on the average size of the polymer chains. The two most common forms of averages used for polymers are the number average molecular weight and weight average molecular weight.
The number average molecular weight (Mn) is the summation of the number...
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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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Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

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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.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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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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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
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Dynamic coarse-graining of polymer systems using mobility functions.

Bing Li1, Kostas Daoulas2, Friederike Schmid1

  • 1Institut für Physik, Johannes Gutenberg-Universität Mainz, 55099 Mainz, Germany.

Journal of Physics. Condensed Matter : an Institute of Physics Journal
|March 10, 2021
PubMed
Summary

We developed a dynamic coarse-graining (CG) method to accurately model polymer fluid dynamics. This approach ensures consistency between microscopic and CG models for better simulation of polymer behavior.

Keywords:
coarse-grainingdynamic density functional theorydynamic structure factordynamicsfrictionmobility functionpolymer simulations

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Area of Science:

  • Polymer Physics
  • Computational Materials Science
  • Soft Matter Physics

Background:

  • Accurate dynamic modeling of polymer fluids is crucial for understanding their behavior.
  • Existing coarse-graining (CG) methods often struggle to maintain dynamic consistency.
  • Bridging length and time scales in polymer simulations remains a challenge.

Purpose of the Study:

  • To develop a dynamic coarse-graining (CG) scheme for mapping heterogeneous polymer fluids onto CG models.
  • To ensure dynamic consistency in the mapping process.
  • To enable accurate simulation of polymer fluid kinetics.

Main Methods:

  • Proposed a dynamic coarse-graining (CG) scheme using a wave-vector dependent mobility function derived from the single-chain dynamic structure factor.
  • Calculated the microscopic reference system's dynamic structure factor.
  • Modified CG dynamics with internal friction parameters to adjust local dynamics without altering static structure.

Main Results:

  • The proposed dynamic CG scheme accurately reproduces order/disorder kinetics in polymer melts.
  • Internal friction parameters were introduced to modify CG monomer dynamics on local scales.
  • Demonstrated successful construction of dynamically consistent CG models for homopolymers with CG chain length N=4.
  • Indicated that longer CG chain lengths are necessary for copolymers.

Conclusions:

  • The developed dynamic CG method provides a dynamically consistent mapping for polymer fluids.
  • The approach is suitable for simulating polymer melt kinetics.
  • The method's effectiveness depends on polymer architecture, with copolymers requiring longer CG chains.