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Related Concept Videos

Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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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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Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

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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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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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Ziegler–Natta Chain-Growth Polymerization: Overview01:17

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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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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Reversible Addition-Fragmentation Chain-Transfer Polymerization in Supercritical CO2: A Review.

Friso G Versteeg1, Francesco Picchioni1

  • 1Department of Chemical Engineering - Product Technology, University of Groningen, Nijenborgh 4, Groningen, 9747 AG, The Netherlands.

Macromolecular Rapid Communications
|September 11, 2024
PubMed
Summary
This summary is machine-generated.

This review explores using supercritical carbon dioxide (scCO2) for cleaner polymerization. While challenges exist in achieving high molar mass, scCO2 offers potential for sustainable, low molar mass polymer production.

Keywords:
controlled radical polymerizationsupercritical CO2

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Area of Science:

  • Polymer Chemistry
  • Green Chemistry

Background:

  • Volatile organic solvents (VOCs) in polymerization pose environmental and health risks.
  • Increasing regulatory pressure necessitates alternatives to traditional VOCs.
  • Supercritical fluids offer a promising avenue for sustainable chemical processes.

Purpose of the Study:

  • To review the application of supercritical carbon dioxide (scCO2) in polymerization.
  • To focus on reversible addition-fragmentation chain-transfer (RAFT) polymerization in scCO2.
  • To assess the feasibility of scCO2 as a greener solvent for polymer synthesis.

Main Methods:

  • Exploration of RAFT polymerization mechanisms in scCO2.
  • Investigation of monomer selection and chain transfer agents (CTAs).
  • Analysis of the role of stabilizers in scCO2 polymerization.

Main Results:

  • RAFT polymerization in scCO2 is influenced by CTA choice, affecting polymer dispersity and molar mass.
  • Stabilizers are critical for controlling polymer properties, except for fluoropolymers.
  • Achieving high molar mass polymers in scCO2 is limited by solubility and precipitation.

Conclusions:

  • Supercritical CO2 shows potential for sustainable, circular production of low molar mass polymers.
  • Further research is needed to overcome limitations for high molar mass polymer synthesis.
  • scCO2 polymerization is a step towards greener chemical processes, though not yet fully green.