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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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Characteristics and Nomenclature of Copolymers01:24

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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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Properties of Enantiomers and Optical Activity02:24

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It is essential to understand the difference between chiral and achiral interactions and the implications thereof in optical activity and their applications. Just as our feet, which are chiral, interact uniquely with chiral objects, such as a pair of shoes, but identically with achiral socks, enantiomers of a molecule exhibit different properties only when they interact with other chiral media. An example of a significant implication from this facet is the phenomenon known as optical activity,...
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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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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.
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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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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Blending as a Strategy to Attain Chiro-Optically Activity Polymers.

Ana Paula Glislere1, Denis Turchetti1, Bruno Nowacki1

  • 1Chemistry Department, Paulo Scarpa Polymer Laboratory (LaPPS), Federal University of Parana, Curitiba, Parana, 81531-990, Brazil.

Macromolecular Rapid Communications
|May 3, 2021
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Summary

Pure polymers lack chiro-optical activity. However, blends with achiral polymers exhibit strong activity due to stable supramolecular structures, suggesting morphology control for active polymers.

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chiral polymerschiro-optical activitycircular dichroismnonlinear optics

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Area of Science:

  • Polymer Science
  • Supramolecular Chemistry
  • Chiroptical Spectroscopy

Background:

  • Chiroptical properties are crucial for advanced material applications.
  • Pure polymers with and without chiral centers often lack inherent chiroptical activity.
  • Understanding structure-property relationships in polymer blends is essential.

Purpose of the Study:

  • To investigate the chiroptical properties of polymer blends composed of chiral and achiral copolymers.
  • To determine the origin of chiroptical activity in these blends.
  • To explore the role of supramolecular morphology in inducing chiroptical behavior.

Main Methods:

  • Synthesis of chiral and achiral copolymers.
  • Preparation of polymer blends with varying compositions.
  • Circular dichroism (CD) spectroscopy analysis.
  • Morphological characterization of supramolecular structures.

Main Results:

  • Pure chiral and achiral polymers showed no chiroptical signal in CD spectra.
  • Blends with achiral polymers as the major component displayed significant chiroptical activity.
  • This activity originated from stable supramolecular structures, independent of blend composition.
  • The number of chiral supramolecular structures varied with blend composition.

Conclusions:

  • Supramolecular morphology is a key factor in achieving chiroptical activity in polymers.
  • Designing stable supramolecular structures offers a viable strategy for creating chiroptical polymers.
  • Blend composition influences the quantity, not the nature, of active supramolecular assemblies.