Fully Recyclable and Remarkably Robust Cross-linked Polyethylene Networks via Direct Free-Radical Copolymerization with Disulfide Dynamic Covalent Bonds

07 May 2025, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Cross-linked polyethylene (PEX) is a commercially important polyolefin thermoset that suffers from non-recyclability due to its permanent cross-links. Herein, we report the first in-reactor synthesis of dynamic covalently cross-linked polyethylene or polyethylene covalent adaptable networks (PE CANs) via free-radical copolymerization of ethylene and bis(2,2,6,6-tetramethyl-4-piperidyl methacrylate) disulfide (BTMA). BTMA is a bifunctional comonomer containing a dissociative dynamic disulfide bond. These PE CANs exhibit high crystallinity, outstanding dimensional stability, high-temperature creep resistance, and robust thermomechanical properties comparable to commercial PEX. Crucially, our PE CANs demonstrate full recovery of cross-link density and thermomechanical performance after recycling. Stress relaxation studies reveal viscoelastic behavior enabled by cross-link exchange but dominated by polymer chain reptation, resulting in activation energies aligned with those of long-chain-branched PE melts. This work presents a novel, scalable method for free-radical copolymerization of recyclable PE CANs, offering a more sustainable alternative to PEX.

Keywords

polyethylene
dynamic
dynamic covalent chemistry
vitrimer
covalent adaptable network
network
PEX
cross-link
stress relaxation

Supplementary materials

Title
Description
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Title
Supporting Information for Fully Recyclable and Remarkably Robust Cross-linked Polyethylene Networks via Direct Free-Radical Copolymerization with Disulfide Dynamic Covalent Bonds
Description
Experimental details, solid-state 1H NMR spectra, FTIR spectra, PE CAN property data, i.e., DSC, DMA, stress relaxation, gel contents, creep.
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