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Related Concept Videos

Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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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...
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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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Polymer Classification: Stereospecificity01:26

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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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Polymer Classification: Architecture01:14

Polymer Classification: Architecture

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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by &#960;-&#960; Stacking Interactions
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Controlling the Polymer Microstructure in Anionic Polymerization by Compartmentalization.

Elisabeth Rieger1, Jan Blankenburg2,3, Eduard Grune2,3

  • 1Max Planck Institute for Polymer Research, 55128, Mainz, Germany.

Angewandte Chemie (International Ed. in English)
|December 15, 2017
PubMed
Summary
This summary is machine-generated.

Researchers created gradient copolymers using emulsion polymerization by controlling monomer separation. Diluting the continuous phase precisely adjusted copolymer composition, enabling tunable gradient structures from random ones.

Keywords:
anionic polymerizationaziridinescompartmentalizationcopolymeruzationemulsions

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Emulsion Polymerization

Background:

  • Controlled synthesis of gradient copolymers is challenging.
  • Anionic copolymerization offers precise control but lacks spatial control.
  • Emulsion systems provide compartmentalization for spatial control.

Purpose of the Study:

  • To develop a method for producing gradient anionic copolymers.
  • To control copolymer composition by manipulating monomer concentrations.
  • To investigate the effect of monomer partitioning on copolymer structure.

Main Methods:

  • Utilized a DMSO-in-cyclohexane emulsion system.
  • Performed living anionic copolymerization of activated aziridines.
  • Controlled monomer D concentration in droplets via continuous phase dilution.
  • Monitored polymerization kinetics using real-time 1H NMR.

Main Results:

  • Achieved selective polymerization within DMSO droplets.
  • Demonstrated tunable copolymer composition by adjusting dilution.
  • Observed a shift in monomer reactivity ratios with dilution.
  • Successfully transitioned from ideal random to gradient copolymer structures.

Conclusions:

  • Emulsion compartmentalization enables spatial control in anionic copolymerization.
  • Dilution of the continuous phase is an effective strategy for gradient copolymer synthesis.
  • This method allows for the creation of adjustable gradient copolymer structures.