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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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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...
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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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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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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 species into...
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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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Grafting-Induced Structural Ordering of Lactide Chains.

Artyom D Glova1, Sofya D Melnikova2, Anna A Mercurieva1

  • 1Institute of Macromolecular Compounds, Russian Academy of Sciences, Bolshoj pr. 31 (V.O.), 199004 St. Petersburg, Russia.

Polymers
|December 15, 2019
PubMed
Summary

Grafted lactide chains in a polymer melt unexpectedly form ordered helical structures at specific lengths. This structural ordering, influenced by graft length and density, is an early stage of crystallization.

Keywords:
dipolar chainslactidemolecular dynamicsnanocompositespolymer brushessimulationsstructural ordering

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Area of Science:

  • Polymer Science
  • Materials Science
  • Computational Chemistry

Background:

  • Polymer brushes are widely used in surface modification and nanotechnology.
  • Understanding the conformational behavior of grafted polymers is crucial for designing advanced materials.
  • The

Purpose of the Study:

  • To investigate the structural behavior of grafted lactide chains in the

Main Methods:

  • Atomistic molecular dynamics simulations were employed to study the grafted layer.
  • Simulations were conducted over microsecond timescales to capture relevant dynamics.
  • Graft lengths were systematically varied to observe their effect on chain structure.

Main Results:

  • Graft length had minimal impact on the backfolding of lactide chains to the grafting surface.
  • Unexpected structural ordering, forming helical fragments, was observed at specific graft lengths (around 10 Kuhn segments).
  • This ordering aligns with experimental data for the alpha crystal of lactide chains.

Conclusions:

  • Both backfolding and structural ordering represent initial stages of crystallization for grafted lactide chains.
  • Unlike conventional polymer brushes, grafted lactide chains can exhibit amorphous or ordered structures.
  • The final structure depends on the interplay between graft length (N) and grafting density (σ).