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Related Concept Videos

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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Actin polymerization occurs through the head-to-tail association of binding sites on monomeric actin or G-actin to form filamentous or F-actin. The polymerization can be divided into three phases ̶  nucleation, elongation, and steady-state phase.
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Step-Growth Polymerization: Overview01:03

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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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Actin Polymerization and Cell Motility01:13

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Actin is a family of globular proteins that are highly abundant in eukaryotic cells. It makes up approximately 1-5% of total cell protein concentration. Actin monomers polymerize to form a complex network of polarized filaments, the actin cytoskeleton, that plays a crucial role in many cellular processes, including cell motility, division, endocytosis, and metastasis of cancer cells.
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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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Radical Chain-Growth Polymerization: Overview01:10

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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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Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization
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Ring-Walking in Catalyst-Transfer Polymerization.

Amanda K Leone1, Peter K Goldberg1, Anne J McNeil1

  • 1Department of Chemistry and Macromolecular Science and Engineering Program , University of Michigan , 930 North University Avenue , Ann Arbor , Michigan 48109-1055 , United States.

Journal of the American Chemical Society
|June 16, 2018
PubMed
Summary
This summary is machine-generated.

Catalyst-transfer polymerization (CTP) offers control over conjugated polymers. Catalyst, ligand, and polymer identity critically influence polymerization livingness and chain-growth behavior, guiding future CTP applications.

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Area of Science:

  • Polymer Chemistry
  • Organic Synthesis
  • Materials Science

Background:

  • Catalyst-transfer polymerization (CTP) is a valuable technique for synthesizing conjugated polymers with precise control over molecular characteristics.
  • The living and chain-growth nature of CTP is known to be sensitive to catalyst and monomer selection.
  • Limited understanding exists regarding how these factors affect the stability and reactivity of key intermediates under polymerization conditions.

Purpose of the Study:

  • To investigate the influence of catalyst, ancillary ligand, and polymer identity on catalyst stability and ring-walking ability in CTP.
  • To develop a straightforward experimental approach for assessing these critical polymerization parameters.
  • To provide insights for expanding CTP to diverse monomer and copolymer systems.

Main Methods:

  • Development of a simple experimental setup to evaluate catalyst stability and ring-walking phenomena.
  • Utilizing in situ-generated polymers to mimic actual polymerization conditions.
  • Systematic variation of ancillary ligands, transition metals, and polymer backbones (poly(thiophene) and poly(phenylene)).

Main Results:

  • Demonstrated that ancillary ligand, metal identity, and polymer type significantly impact CTP outcomes.
  • Observed efficient catalyst ring-walking over extended distances in poly(thiophene) systems across all tested catalysts.
  • Highlighted distinct trends for poly(phenylene) that underscore the differential roles of transition metals and ancillary ligands in controlling polymerization.

Conclusions:

  • The stability and reactivity of intermediates in CTP are strongly dictated by the interplay between the catalyst system and the growing polymer chain.
  • Understanding these structure-property relationships is essential for optimizing CTP for various monomers.
  • The findings provide a foundation for the rational design of catalysts and polymerization conditions for novel conjugated polymers.