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Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)

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.
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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.
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Related Experiment Video

Updated: Sep 23, 2025

Fabricating Degradable Thermoresponsive Hydrogels on Multiple Length Scales via Reactive Extrusion, Microfluidics, Self-assembly, and Electrospinning

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Molecularly Designed Additives for Chemically Deconstructable Thermosets without Compromised Thermomechanical

K E L Husted¹, P Shieh¹, D J Lundberg²

¹Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

ACS Macro Letters

|May 13, 2022

Summary

New strand-cleaving crosslinker (SCC) additives enable chemically deconstructable thermosets. This innovation maintains high glass transition temperatures (Tg) and enhances sustainability without compromising material performance.

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Area of Science:

Polymer Chemistry
Materials Science
Sustainable Chemistry

Background:

Thermoset polymers like polydicyclopentadiene (pDCPD) offer excellent thermomechanical properties but are difficult to recycle.
Existing methods to introduce chemical deconstruction into pDCPD compromise its glass transition temperature (Tg).

Purpose of the Study:

To develop novel "drop-in" additives for thermosets that enable chemical deconstruction without sacrificing thermomechanical performance.
To introduce strand-cleaving crosslinker (SCC) additives into pDCPD to create cleavable network junctions.

Main Methods:

Synthesized and incorporated "strand-cleaving crosslinker" (SCC) additives into polydicyclopentadiene (pDCPD) networks.
Evaluated the thermomechanical properties, specifically glass transition temperature (Tg), of the modified pDCPD.
Assessed the deconstruction efficiency and product solubility under mild conditions.

Main Results:

pDCPD samples with 10% v/v SCC additives exhibited efficient deconstruction into soluble products under mild conditions.
The SCC-modified pDCPD showed a 48 °C higher Tg compared to pDCPD made with cleavable comonomers.
The Tg of SCC-modified pDCPD was equivalent to virgin pDCPD, indicating no compromise in thermomechanical performance.

Conclusions:

Strand-cleaving crosslinker (SCC) additives provide a viable strategy for creating chemically deconstructable thermosets.
This approach overcomes the trade-off between deconstruction capability and thermomechanical properties in thermoset materials.
The SCC concept offers a generalizable method for designing sustainable thermosets with tunable deconstruction.