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Related Concept Videos

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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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.4K
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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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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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...
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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this...
2.8K
Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

2.2K
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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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Entropic Origin of Polymer Nucleation at Amorphous Solid Interfaces.

Ming Wang1,2, Zijian Song1,3, Guoming Liu1,2

  • 1Institute of Chemistry, Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Chinese Academy of Sciences, Beijing 100190, China.

Physical Review Letters
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Summary
This summary is machine-generated.

Polymer crystallization nucleation at interfaces is driven by chain entropy loss at weak interactions. Stronger interactions favor homogeneous nucleation over surface-induced polymer crystallization.

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Area of Science:

  • Polymer science
  • Materials science
  • Physical chemistry

Background:

  • Interfaces significantly influence physical, chemical, and biological processes.
  • Polymer crystallization frequently initiates at solid interfaces (heterogeneous nucleation) due to a lower nucleation barrier.
  • Chain conformations and dynamics near interfaces differ substantially from the bulk.

Purpose of the Study:

  • To distinguish between surface and homogeneous nucleation mechanisms in polymers.
  • To investigate the role of interfacial interactions and polymer chain entropy in nucleation.

Main Methods:

  • Utilized a nanopore-confined system to study polymer nucleation.
  • Performed comprehensive crystal orientation analysis to differentiate nucleation scenarios.

Main Results:

  • Surface-induced nucleation is primarily governed by an entropic effect.
  • This entropic effect arises from the loss of conformational entropy as polymer chains flatten at interfaces with weak interactions.
  • Homogeneous nucleation becomes dominant when interfacial interactions are strong.

Conclusions:

  • The study elucidates the distinct mechanisms driving surface versus homogeneous nucleation in polymers.
  • Interfacial energy and polymer chain conformational entropy are key factors determining nucleation pathways.
  • Findings provide insights into controlling polymer crystallization through interface engineering.