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Related Concept Videos

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...
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...
Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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 generated carbocation,...
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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...
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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 catalyst, high molecular...

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Microwave-assisted Functionalization of Poly(ethylene glycol) and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation
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Mean field theory for a reversibly crosslinked polymer network.

Daming Li1, Thomas Gruhn, Heike Emmerich

  • 1Materials and Process Simulation (MPS), University of Bayreuth, D-95440 Bayreuth, Germany. lidaming@sjtu.edu.cn

The Journal of Chemical Physics
|July 19, 2012
PubMed
Summary

This study introduces a mean field theory for reversibly crosslinked polymer blends. The model shows that varying monomer interactions can lead to phase separation of both polymer types and crosslinked structures.

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Published on: September 26, 2016

Area of Science:

  • Polymer Physics
  • Materials Science
  • Statistical Mechanics

Background:

  • Reversibly crosslinked polymers offer tunable material properties.
  • Understanding phase behavior in polymer blends is crucial for material design.
  • Mean field theories provide a framework for predicting polymer blend thermodynamics.

Purpose of the Study:

  • To develop a mean field theory for polymer melts and solutions with reversible crosslinks.
  • To investigate the influence of crosslink strength and monomer interactions on phase separation.
  • To analyze the behavior of A+B+AB polymer blends and homopolymer solutions.

Main Methods:

  • Formulation of a mean field theory model.
  • Analysis of reversible crosslinks between copolymer monomers.
  • Mathematical modeling of polymer blend and solution thermodynamics.

Main Results:

  • The model recovers the standard mean field theory for non-crosslinked systems when crosslink strength is zero.
  • In A+B+AB blends, differing monomer interactions (ω(A) ≠ ω(B)) induce co-segregation of crosslinked and non-crosslinked polymers alongside nanophase separation.
  • In homopolymer solutions, macroscopic phase separation occurs under specific conditions of high Flory-Huggins parameter, high crosslink strength, or low polymer volume fraction/chain length.

Conclusions:

  • Reversible crosslinks significantly influence the phase behavior of polymer blends and solutions.
  • The interplay between crosslinking and monomer-monomer interactions dictates the degree and type of phase separation.
  • The developed theory provides insights into designing materials with controlled nanostructures and macroscopic separation.