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Related Concept Videos

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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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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Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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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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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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Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Modeling the competition between phase separation and polymerization under explicit polydispersity.

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Polymerization-induced phase separation is modeled using a polymerizing Cahn-Hilliard approach. Faster polymerization can delay phase separation due to molecular weight buildup, impacting polymer blend morphology.

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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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Area of Science:

  • Polymer Science
  • Materials Science
  • Chemical Engineering

Background:

  • Phase separation in polymer blends dictates material properties.
  • Polymerization-induced phase separation couples reaction kinetics with morphology development.
  • Controlling phase separation is crucial for tailoring polymer materials.

Purpose of the Study:

  • To develop and apply a phase-field model for polymerization-induced phase separation in polymer blends.
  • To investigate the interplay between phase separation dynamics and polymerization kinetics.
  • To analyze the influence of polydispersity and unequal reaction rates on phase separation behavior.

Main Methods:

  • Developed a polymerizing Cahn-Hilliard (pCH) phase-field model.
  • Explicitly incorporated polydispersity to account for varying molecular weights and diffusion rates.
  • Validated the model against Carothers predictions, Flory-Huggins theory, and classical spinodal decomposition.

Main Results:

  • The pCH model accurately predicts polymerization kinetics and phase separation behavior.
  • High incompatibility (high chi) correlates phase separation strength with kinetics.
  • Increasing reaction rates initially accelerates phase separation, but further increases can delay it due to diffusion-polymerization competition.

Conclusions:

  • The model provides fundamental insights into polymerization-induced phase separation.
  • Faster polymerization can lead to delayed phase separation due to the accumulation of high molecular weight species.
  • This understanding is critical for controlling morphology and properties in polymer blends.