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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

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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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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.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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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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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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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Photoinduced Initiation of Olefin Polymerization: Enabling Spatial Control with Light.

Jordan M Kaiser1, Justin M Burroughs1, Brian K Long1

  • 1Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, United States.

Journal of the American Chemical Society
|November 8, 2022
PubMed
Summary
This summary is machine-generated.

Researchers developed photoinduced initiation of olefin polymerization (PIOP) for spatial control. This method uses photoacid generators and controlled light to activate catalysts, enabling precise polymer synthesis for polyolefins.

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Organic Synthesis

Background:

  • Polyolefins are the most produced plastics globally.
  • Existing precatalyst activation methods lack spatial control in olefin polymerization.
  • Developing controlled polymerization is key for advanced material properties and applications.

Purpose of the Study:

  • To introduce a novel, spatially controlled olefin polymerization method.
  • To demonstrate the efficacy of photoinduced initiation of olefin polymerization (PIOP).
  • To enable precise control over polymer architecture and properties.

Main Methods:

  • Utilized photoacid generators (PAGs) for catalyst activation.
  • Employed controlled irradiation to initiate polymerization.
  • Applied the PIOP method to solution-based polymerization of ethylene and alpha-olefins.

Main Results:

  • Successfully demonstrated PIOP for ethylene and alpha-olefin polymerization.
  • Achieved spatial control over the polymerization process.
  • Showcased potential for extending PIOP to heterogeneous polymerization of gaseous monomers.

Conclusions:

  • PIOP offers a new pathway for controlled olefin polymerization.
  • This technique provides unprecedented synthetic control.
  • PIOP has the potential to broaden industrial applications in plastics manufacturing.