Related Experiment Video
Updated: Dec 19, 2025
10:22
Designed for Molecular Recycling: A Lignin-Derived Semi-aromatic Biobased Polymer
Published on: November 30, 2020
3.8K
Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency
Antoine Tardy1, Noémie Gil1, Christopher M Plummer1
1Aix-Marseille Univ, CNRS, Institut de Chimie Radicalaire UMR 7273, Marseille, France.
Angewandte Chemie (International Ed. in English)
|June 5, 2020
Summary
Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) can now be predicted using computational methods. This advance allows for the design of new CKAs for biodegradable polyesters in biomedical applications.
Area of Science:
- Polymer Chemistry
- Materials Science
Background:
- Radical ring-opening polymerization (rROP) offers a mild route to polyesters, with copolymers exhibiting biodegradability.
- Developing efficient cyclic ketene acetal (CKA) monomers is challenging due to competing ring-opening and ring-retaining pathways.
Purpose of the Study:
- To investigate the rROP of model CKA monomers.
- To develop in silico methods for predicting CKA ring-opening ability.
Main Methods:
- Density Functional Theory (DFT) calculations.
- Kinetic modeling using PREDICI software.
Main Results:
- Demonstrated the ability to predict the ring-opening behavior of CKA monomers computationally.
- Identified key factors influencing the competition between ring-opening and ring-retaining propagation.
Conclusions:
- Computational tools can now guide the design of novel CKA monomers for controlled polymerization.
- This predictive capability is crucial for advancing biodegradable polyester synthesis for biomedical applications.
Related Concept Videos
02:35Free-Radical Chain Reaction and Polymerization of Alkenes
9.2K
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.
9.2K
01:20Types of Step-Growth Polymers: Polyesters
2.5K
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.
Polyesters are commonly prepared from terephthalic acid and ethylene glycol; the crude product is known as poly(ethylene terephthalate) or PET. However, polyesters are synthesized industrially by transesterification of dimethyl terephthalate with ethylene glycol at 150 °C. The two reactants and the polymer...
Polyesters are commonly prepared from terephthalic acid and ethylene glycol; the crude product is known as poly(ethylene terephthalate) or PET. However, polyesters are synthesized industrially by transesterification of dimethyl terephthalate with ethylene glycol at 150 °C. The two reactants and the polymer...
2.5K
00:53Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
2.1K
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...
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...
2.1K
01:17Radical Chain-Growth Polymerization: Chain Branching
2.3K
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...
2.3K
01:10Radical Chain-Growth Polymerization: Overview
3.0K
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...
3.0K
01:09Radical Chain-Growth Polymerization: Mechanism
3.2K
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 species into...
3.2K