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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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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

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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: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
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Types of Step-Growth Polymers: Polyesters01:20

Types of Step-Growth Polymers: Polyesters

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The introduction of polyesters has brought major development to the textile industry. The wrinkle-free behavior of polyester blends has eliminated the need for starching and ironing clothes.
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Polymer Classification: Architecture01:14

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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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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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Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Thermodynamic limits of the depolymerization of poly(olefin)s using mechanochemistry.

Yuchen Chang1, Van Son Nguyen1, Adrian H Hergesell2

  • 1School of Chemical & Biomolecular Engineering, Georgia Institute of Technology Atlanta Georgia 30332 USA carsten.sievers@chbe.gatech.edu.

RSC Mechanochemistry
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Summary

Mechanochemistry offers plastic recycling potential, but polyolefins like polyethylene and polypropylene depolymerize slowly due to thermodynamic limits. Energy input and monomer volatility significantly impact reaction efficiency in ball mills.

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Area of Science:

  • Polymer Science
  • Mechanochemistry
  • Chemical Recycling

Background:

  • Mechanochemistry is a promising method for chemical recycling of plastics.
  • Depolymerization of commodity plastics to monomers is achievable via mechanochemistry.
  • Poly(olefin)s represent a large fraction of global plastic waste, but their mechanochemical depolymerization is slow.

Purpose of the Study:

  • To rationalize the reactivity of poly(styrene), poly(ethylene), and poly(propylene) in mechanochemical depolymerization.
  • To investigate thermodynamic limitations affecting polymer depolymerization rates.
  • To discuss monomer removal via gas stream purging and its thermodynamic constraints.

Main Methods:

  • Analysis of polymer reactivity in laboratory-scale ball mill reactors.
  • Thermodynamic analysis of depolymerization by free radical depropagation.
  • Evaluation of phase partitioning equilibria for monomer removal via purge gas.

Main Results:

  • Polymer reactivity is governed by thermodynamic limitations of depolymerization.
  • Energy input in vibratory ball mills is sufficient for poly(styrene) but not for poly(ethylene) or poly(propylene).
  • Styrene removal is hindered by low volatility, unlike propylene and ethylene.

Conclusions:

  • Thermodynamic factors dictate the efficiency of mechanochemical plastic recycling.
  • Reactor design must account for energy input and monomer volatility for effective polyolefin depolymerization.
  • Understanding these limitations is crucial for developing efficient mechanocatalytic processes.