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Radical Chain-Growth Polymerization: Chain Branching01:17

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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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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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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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Anionic Chain-Growth Polymerization: Overview01:20

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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

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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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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Self assembled linear polymeric chains with tuneable semiflexibility using isotropic interactions.

Alex Abraham1, Apratim Chatterji1

  • 1Department of Physics, IISER-Pune, Dr. Homi Bhaba Road, Pune 411008, India.

The Journal of Chemical Physics
|April 23, 2018
PubMed
Summary
This summary is machine-generated.

We developed a novel potential for self-assembling polymers. This potential allows control over polymer chain length, flexibility, and branching, enabling tunable directional interactions from simple spherical potentials.

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Area of Science:

  • Soft Matter Physics
  • Polymer Science
  • Colloid Science

Background:

  • Spherical symmetric potentials typically lead to isotropic interactions.
  • Achieving directional self-assembly from isotropic potentials is a significant challenge.
  • Understanding equilibrium polymer formation is crucial for materials science.

Purpose of the Study:

  • To introduce a novel two-body spherically symmetric potential for self-assembling linear semiflexible polymeric chains.
  • To demonstrate control over polymer properties like persistence length and branching.
  • To investigate the phase behavior and self-organization of these emergent polymers.

Main Methods:

  • Development of a specific two-body isotropic potential function.
  • Computational simulations to observe particle self-assembly and polymer formation.
  • Analysis of chain length distributions, phase transitions, and structural organization.

Main Results:

  • Particles self-assemble into linear, semiflexible polymer chains with exponential length distributions.
  • Tunable control over polymer persistence length and branching is achieved by adjusting potential parameters.
  • Observed phase transitions include a disordered phase, an ordered line-hexagonal phase, and a branched gel-like phase.
  • An intermediate nematic phase was identified with a modified potential.

Conclusions:

  • The proposed potential effectively generates equilibrium polymers with tunable properties from simple isotropic interactions.
  • This model provides a computationally efficient method to study long polymer dynamics and colloidal self-assembly.
  • The findings offer a pathway for experimental tuning of colloidal interactions to create self-assembling polymer chains.