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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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Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
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Although gaseous molecules travel at tremendous speeds (hundreds of meters per second), they collide with other gaseous molecules and travel in many different directions before reaching the desired target. At room temperature, a gaseous molecule will experience billions of collisions per second. The mean free path is the average distance a molecule travels between collisions. The mean free path increases with decreasing pressure; in general, the mean free path for a gaseous molecule will be...
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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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For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
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Radical Chain-Growth Polymerization: Mechanism01:09

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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...
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A simulation study on the subdiffusion of polymer chains in crowded environments containing nanoparticles.

Rong-Xing Lu1, Jian-Hua Huang1, Meng-Bo Luo2

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Polymer chains exhibit subdiffusion in crowded environments with attractive nanoparticles (NPs). Subdiffusion transitions to normal diffusion as polymer concentration increases, influenced by NP concentration and size.

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Area of Science:

  • Polymer Physics
  • Soft Matter Physics
  • Computational Materials Science

Background:

  • Polymer chains in crowded environments often display subdiffusive behavior.
  • Understanding diffusion mechanisms is crucial for polymer science and materials engineering.

Purpose of the Study:

  • Investigate the conditions leading to subdiffusion of polymer chains in crowded environments.
  • Analyze the influence of attractive nanoparticles (NPs) on polymer chain diffusion.

Main Methods:

  • Utilized molecular dynamics simulations.
  • Studied polymer chains in environments with randomly distributed, immobile, attractive nanoparticles (NPs).

Main Results:

  • Subdiffusion occurs at low polymer chain concentrations (cp).
  • A transition to normal diffusion is observed above a critical concentration, influenced by NP concentration and size.
  • High NP concentration and small NP size enhance subdiffusion.

Conclusions:

  • Subdiffusion is attributed to strong adsorption of polymer chains on attractive NPs.
  • NP-exchange diffusion dominates subdiffusion, while adsorption-and-desorption governs normal diffusion.