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Related Concept Videos

Characteristics and Nomenclature of Copolymers01:24

Characteristics and Nomenclature of Copolymers

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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Cationic Chain-Growth Polymerization: Mechanism00:57

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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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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: 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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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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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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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...
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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Heat capacity anomaly in a self-aggregating system: Triblock copolymer 17R4 in water.

Lorenzo V Dumancas1, David E Simpson1, D T Jacobs1

  • 1Department of Physics, The College of Wooster, Wooster, Ohio 44691, USA.

The Journal of Chemical Physics
|May 10, 2015
PubMed
Summary

This study investigates the phase behavior of reverse Pluronic copolymer 17R4 in water. Researchers observed a heat capacity anomaly at the critical point, indicating a second-order phase transition in copolymer-water interactions.

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

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Area of Science:

  • Polymer Science
  • Physical Chemistry
  • Thermodynamics

Background:

  • Reverse Pluronic triblock copolymer 17R4 (PPO14-PEO24-PPO14) exhibits complex phase behavior in water.
  • This includes micellization and liquid-liquid phase separation with a lower consolute critical point.

Purpose of the Study:

  • To investigate the heat capacity anomalies associated with phase transitions in aqueous solutions of Pluronic 17R4.
  • To characterize the thermodynamic behavior near the critical point and micellization phenomena.

Main Methods:

  • Adiabatic calorimetry was employed to measure heat capacity as a function of temperature.
  • Experiments were conducted for three distinct compositions: critical, sub-critical, and near the micellization-cloud point intersection.

Main Results:

  • A heat capacity anomaly, indicative of a second-order phase transition, was observed at the critical composition for the first time in Pluronic/water systems.
  • The onset of micellization was clearly identified for all compositions, though micelle formation was broad and incomplete above the cloud point.
  • Integrated heat capacity yielded an enthalpy smaller than that obtained from van't Hoff analysis.

Conclusions:

  • The observed heat capacity anomaly confirms a second-order phase transition driven by copolymer-water interactions.
  • Micellization in Pluronic 17R4/water systems is a complex process influenced by phase separation.
  • Discrepancies in enthalpy values highlight the intricate nature of micelle formation in these systems.