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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

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: Acyclic Diene Metathesis (ADMET)00:53

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

1.9K
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...
1.9K
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

2.6K
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

Radical Chain-Growth Polymerization: Overview

2.4K
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...
2.4K
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

3.3K
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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The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry
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The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry

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Using Redox-Switchable Polymerization Catalysis to Synthesize a Chemically Recyclable Thermoplastic Elastomer.

Jiangwei Liu1, Sarah E Blosch2, Anastasia S Volokhova2

  • 1Department of Chemistry, Boston College, Eugene F. Merkert Chemistry Center, 2609 Beacon Street, Chestnut Hill, MA 02467, USA.

Angewandte Chemie (International Ed. in English)
|January 3, 2024
PubMed
Summary

Chemically recyclable thermoplastic elastomers were synthesized using a redox-switchable catalyst. This innovation allows for the creation of flexible triblock copolymers with potential for sustainable material applications.

Keywords:
Chemical RecyclingRedox Switchable CatalysisThermoplastic ElastomerTriblock Copolymer

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Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst
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Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

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The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry
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Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst
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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Sustainable Chemistry

Background:

  • Thermoplastic elastomers (TPEs) are crucial in various industries.
  • Developing chemically recyclable TPEs remains a significant challenge.
  • Current TPEs often lack efficient end-of-life recycling pathways.

Purpose of the Study:

  • To synthesize novel, chemically recyclable triblock copolymers.
  • To create TPEs with tunable flexibility and thermomechanical properties.
  • To establish a sustainable synthesis and recycling process for TPEs.

Main Methods:

  • Utilized a redox-switchable iron-based catalytic system.
  • Synthesized triblock copolymers with poly(lactic acid) (PLA) end blocks and a flexible poly(tetrahydrofuran-co-cyclohexene oxide) (poly(THF-co-CHO)) mid-block.
  • Employed orthogonal reactivity for single-flask copolymer synthesis from monomers.

Main Results:

  • Achieved synthesis of triblock copolymers with properties resembling TPEs.
  • Demonstrated enhanced flexibility compared to poly(l-lactic acid) (PLLA).
  • Observed a rubbery plateau from -60 to 40°C, indicating TPE-like behavior.
  • Found increased flexibility with higher THF content in the mid-block.
  • Created a stereocomplex blend of PLLA and poly(d-lactic acid) (PDLA) end blocks to further enhance flexibility.
  • Successfully depolymerized the copolymers using FeCl3 and ZnCl2/PEG under reactive distillation.

Conclusions:

  • Developed a novel class of chemically recyclable triblock copolymers.
  • The catalytic system enables efficient synthesis of TPEs with tunable properties.
  • The materials exhibit excellent flexibility and thermomechanical performance.
  • The demonstrated depolymerization confirms the sustainability and recyclability of these TPEs.