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Related Concept Videos

Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

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...
Polymers: Molecular Weight Distribution01:10

Polymers: Molecular Weight Distribution

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.
Determination of Molar Masses of Polymers II01:27

Determination of Molar Masses of Polymers II

Polymer samples typically consist of macromolecular chains with a distribution of lengths, resulting in a range of molar masses rather than a single discrete value. Conventional descriptors such as the number-average molar mass and weight-average molar mass quantify this distribution but do not fully capture polymer behavior in solution..The viscosity-average molar mass provides a more realistic description of polymer behavior in solution because it accounts for the enhanced contribution of...
Determination of Molar Masses of Polymers I01:24

Determination of Molar Masses of Polymers I

Polymerization produces macromolecules with a range of chain lengths due to the random nature of molecular growth processes. As chains form and terminate at different stages, a single polymer sample contains molecules of varying sizes rather than a uniform structure. This variability is described using average molar masses and distribution-related parameters, which together provide a comprehensive understanding of polymer characteristics.The distribution of molar masses plays a critical role in...
Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

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...
Polymers: Defining Molecular Weight01:01

Polymers: Defining Molecular Weight

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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Continuum electrostatics for electronic structure calculations in bulk amorphous polymers: application to

James H McAliley1, Christopher P O'Brien, David A Bruce

  • 1Department of Chemical and Biomolecular Engineering, Clemson University, Clemson, South Carolina 29634-0909, USA.

The Journal of Physical Chemistry. A
|July 17, 2008
PubMed
Summary

Estimating polylactide (PLA) bond rotation energetics using computational methods reveals challenges in simulating bulk polymer environments. Current techniques require refinement for accurate condensed-phase polymer modeling.

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Area of Science:

  • Computational Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Understanding polymer chain dynamics is crucial for predicting material properties.
  • Electron density functional theory (DFT) and self-consistent reaction field (SCRF) are common computational tools.
  • Accurately modeling condensed-phase environments for polymers presents significant challenges.

Purpose of the Study:

  • To estimate the bond rotational energy landscapes of polylactide (PLA) oligomers.
  • To evaluate the applicability of the SCRF method for simulating condensed-phase polymer environments.
  • To assess the impact of bulk phase reaction field calculations on polymer energetics.

Main Methods:

  • Density Functional Theory (DFT) at the B3LYP/6-31G** level.
  • Self-Consistent Reaction Field (SCRF) method for condensed-phase simulation.
  • Rotational Isomeric States (RIS) calculations.

Main Results:

  • The SCRF method's application to bulk amorphous polymers is difficult, particularly regarding solvent probe radius selection.
  • Accounting for bulk phase reaction fields affects bond rotational energetics and the characteristic ratio.
  • Current computational methods for bulk polymer environments are not well-suited.

Conclusions:

  • Existing computational approaches for simulating bulk polymer environments need improvement.
  • Further development is required for accurate modeling of condensed-phase polymer systems.
  • This study highlights limitations in current theoretical methods for polymer simulations.