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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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Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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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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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

2.1K
The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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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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Characteristics and Nomenclature of Copolymers01:24

Characteristics and Nomenclature of Copolymers

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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Toughening CO2 -Derived Copolymer Elastomers Through Ionomer Networking.

Kam C Poon1, Georgina L Gregory1, Gregory S Sulley1

  • 1Chemistry Research Laboratory, Department of Chemistry, University of Oxford, Oxford, OX1 3TA, UK.

Advanced Materials (Deerfield Beach, Fla.)
|May 18, 2023
PubMed
Summary

New thermoplastic elastomers (TPEs) are made from recycled carbon dioxide (CO2) and biomass. Metal-carboxylate functionalization significantly enhances their mechanical strength and elasticity for advanced applications.

Keywords:
bio-derived materialscarbon dioxideepoxideionomerslactonepolycarbonatepolyesterring-opening copolymerizationring-opening polymerizationthermoplastic elastomers

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Area of Science:

  • Polymer Chemistry
  • Materials Science
  • Sustainable Chemistry

Background:

  • Carbon dioxide (CO2) utilization via ring-opening copolymerization (ROCOP) offers a sustainable route for polycarbonate synthesis.
  • While CO2-based polycarbonates are accessible, their material properties and potential as thermoplastic elastomers (TPEs) remain underexplored.
  • Integrating biomass-derived monomers with CO2-based polymers presents opportunities for novel material development.

Purpose of the Study:

  • To develop new CO2-derived thermoplastic elastomers (TPEs) with enhanced mechanical properties.
  • To establish a general method for augmenting the tensile strength and Young's modulus of these TPEs.
  • To investigate the structure-property relationships of functionalized CO2-based polycarbonates.

Main Methods:

  • Synthesis of ABA triblock copolymers combining CO2-derived poly(carbonate) (A-block) and poly(ε-decalactone) (B-block).
  • Selective functionalization of the poly(carbonate) blocks with various metal-carboxylates (Na, Mg, Ca, Zn, Al).
  • Characterization of thermal properties (glass transition temperature, Tg) and mechanical performance (tensile strength, Young's modulus, elongation at break, creep resistance).

Main Results:

  • The developed TPEs exhibit tunable thermal and mechanical properties based on metal-carboxylate functionalization.
  • Young's modulus increased over 50-fold and tensile strength increased 21-fold compared to the pristine block polymers.
  • The enhanced elastomers maintained excellent elastic recovery, broad operating temperatures (-20 to 200 °C), and high creep resistance.
  • The functionalized polymers contained less than 1 wt% metal and remained recyclable.

Conclusions:

  • Metal-carboxylate functionalization is an effective strategy to significantly enhance the mechanical properties of CO2-derived TPEs without redesigning the polymer backbone.
  • These novel TPEs offer a promising sustainable alternative to petrochemical elastomers.
  • Potential applications include medicine, robotics, and electronics, leveraging their tunable properties and recyclability.