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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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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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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 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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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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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 Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials.

Antoine Tardy1, Julien Nicolas2, Didier Gigmes1

  • 1Aix Marseille Univ , CNRS, Institut de Chimie Radicalaire UMR 7273, campus Saint Jérôme, Avenue Escadrille Normandie-Niemen, Case 542, 13397 Marseille Cedex 20, France.

Chemical Reviews
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Summary
This summary is machine-generated.

Radical ring-opening polymerization (rROP) enables creating polymers with unique backbone functionalities. This review explores rROP monomers, mechanisms, copolymerization, and applications like degradable materials.

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Area of Science:

  • Polymer Chemistry
  • Materials Science

Background:

  • Cyclic monomers with vinyl or exomethylene groups undergo radical ring-opening polymerization (rROP).
  • rROP combines benefits of ring-opening and radical polymerization, yielding polymers with backbone functionalities.
  • This process offers a robust method for synthesizing polymers with embedded heteroatoms.

Purpose of the Study:

  • To provide a comprehensive review of radical ring-opening polymerization (rROP).
  • To detail monomers, mechanisms, and copolymerization strategies involving rROP.
  • To highlight applications and alternatives for rROP in material design.

Main Methods:

  • Review of existing literature on radical ring-opening polymerization.
  • Analysis of monomer types and polymerization parameters influencing rROP.
  • Examination of copolymerization techniques and material applications.

Main Results:

  • Identification of various cyclic monomers suitable for rROP.
  • Elucidation of key parameters governing the rROP mechanism.
  • Demonstration of rROP's utility in creating copolymers and functional materials.
  • Exploration of applications in low shrinkage and degradable materials.

Conclusions:

  • Radical ring-opening polymerization is a versatile technique for polymer synthesis.
  • rROP facilitates the creation of advanced polymers with tailored properties and applications.
  • The review provides insights into rROP, its copolymers, and alternatives for degradable materials.