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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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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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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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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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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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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Mechanically Activated Solid-State Radical Polymerization and Cross-Linking via Piezocatalysis.

Mitchell D Nothling1, John E Daniels2, Yen Vo1

  • 1School of Chemistry, University of New South Wales, 2052, Sydney, NSW, Australia.

Angewandte Chemie (International Ed. in English)
|March 15, 2023
PubMed
Summary
This summary is machine-generated.

Mechanical force can initiate chemical reactions using piezoelectric barium titanate (BaTiO3) nanoparticles. This process generates reactive hydroxyl radicals (⋅OH) to drive solid-state polymerization, offering a new synthesis route.

Keywords:
Ball MillingFree Radical PolymerizationMechanochemistryMechanoredoxPiezocatalysis

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Area of Science:

  • Solid-state chemistry
  • Materials science
  • Polymer chemistry

Background:

  • Piezocatalysis converts mechanical energy into chemical potential.
  • Piezoelectric materials can drive redox reactions under mechanical load.
  • Solid-state polymerization offers advantages over traditional solution-based methods.

Purpose of the Study:

  • To demonstrate the initiation of solid-state free radical polymerization using piezoelectric barium titanate (BaTiO3) nanoparticles.
  • To investigate the mechanism of radical generation and polymerization initiation under mechanical stress.
  • To explore the potential of mechanoredox catalysis for solid-state synthesis.

Main Methods:

  • Activation of BaTiO3 nanoparticles via ball milling, impact, or compressive loading.
  • Generation of hydroxyl radicals (⋅OH) through mechanoredox catalysis.
  • Initiation of polymerization of acrylamide, acrylate, methacrylate, and styrenic monomers in the solid state.

Main Results:

  • Mechanical activation of BaTiO3 nanoparticles produced reactive hydroxyl radicals (⋅OH).
  • These radicals initiated free radical chain growth and crosslinking of solid monomers.
  • Control experiments highlighted the essential role of chemisorbed water on the BaTiO3 surface.

Conclusions:

  • Piezoelectric BaTiO3 nanoparticles can transduce mechanical energy into reactive radical species.
  • Mechanoredox catalysis involving chemisorbed water is key to radical generation.
  • Force-induced radical production offers a novel pathway for solid-state radical synthesis.