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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to 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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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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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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Polymers: Molecular Weight Distribution01:10

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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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Olefin Metathesis Polymerization: Overview01:13

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
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Insights into Chemically Fueled Supramolecular Polymers.

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Chemically fueled supramolecular polymerization uses molecules activated by chemical fuels to form polymers. This study models these systems, revealing possibilities for sustained oscillations in cooperative polymerization.

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Area of Science:

  • Supramolecular chemistry
  • Polymer science
  • Chemical kinetics

Background:

  • Chemical fuels can control supramolecular polymerization in space and time.
  • Artificial examples of chemically controlled supramolecular polymerization are emerging.
  • Biology effectively utilizes fuel-driven self-assembly and disassembly.

Purpose of the Study:

  • To categorize existing literature examples of chemically fueled supramolecular polymerization.
  • To develop mathematical models for transient activation and assembly in these systems.
  • To explore the potential for sustained oscillations in cooperative supramolecular polymerization.

Main Methods:

  • Literature review and categorization into four regimes based on kinetics and fuel equivalents.
  • Development of mathematical models, starting with activation/deactivation rates.
  • Inclusion of isodesmic and cooperative self-assembly models.
  • Analysis of conditions leading to sustained oscillations in cooperative systems.

Main Results:

  • Four distinct regimes of chemically fueled supramolecular polymerization were identified.
  • Models were developed for transient activation and transient self-assembly processes.
  • Sustained oscillations were demonstrated to be possible in cooperative supramolecular polymerization.
  • Mechanistic insights into oscillatory behavior were provided.

Conclusions:

  • Chemically fueled supramolecular polymerization offers controllable assembly and disassembly.
  • Mathematical modeling is crucial for understanding the kinetics of these systems.
  • Sustained oscillations represent a novel dynamic behavior in artificial supramolecular polymers.
  • Further quantification of kinetic parameters is encouraged for future research.