Temperature and Pressure Effects on the Dynamics of Elastomeric Dioxaborolane Vitrimers
Abstract
We report the synthesis, and the thermal, viscoelastic and dynamic properties of a series of dioxaborolane-based poly(n-butyl methacrylate) (PBMA) vitrimers, as a function of molar mass and cross-linking density. By combining calorimetry, dielectric spectroscopy and rheology, we explored the different characteristic temperatures that influence the dynamics of vitrimers. Three main processes could be identified by dielectric spectroscopy, the local β-process, the segmental α-process and the merged αβ-process at higher temperatures. Pressure was employed to examine their sensitivity through an apparent activation volume. We found that the local β-process was only weakly affected by pressure, and that the rubber-to-glass temperature continuously increased with vitrimer cross-linking density. Our results revealed that the dynamic bonds in vitrimers contribute to an effective unit of relaxation (e.g. an effective segment) that is larger than that in the corresponding homopolymer. In addition, the ratio of activation energies at constant volume and at constant pressure revealed that the segmental dynamics in the vitrimers is controlled by intra-molecular barriers. The viscoelastic properties are influenced by the topology freezing temperature, TV, separating segmental-controlled dynamics at lower temperatures from the bond exchange mechanism at higher temperatures initiating the flow. The derivative approach applied to the viscoelastic shift factors was found to be a practical method to locate TV. In the vitrimers, the bond exchange mechanism had a high apparent activation energy (E ∼ 90 kJ/mol) similar to that of the segmental dynamics. We present the first high-pressure investigation of the relaxation dynamics in vitrimers, elucidating the origin of the segmental process and re-defining the fundamental effective unit of relaxation.
Related
- Libron-phonon coupling and hydrogen-bond dynamics in the vacancy-ordered perovskite (NH4)2SnCl6: a temperature- and pressure-dependent Raman study
- Temperature dependence of the Casimir pressure on two graphene sheets placed on a substrate
- Analysis, thermodynamics, and a numerical solver for a pressure-temperature equilibrium closure of the four-equation model
- Multimodal Visual Sensing of Temperature and Pressure: From Spectroscopic Readout to Multiple Linear Regression-Enhanced RGB Analysis
- Extending the operating window of scanning electron microscopy through an integrated electron-optical architecture for high-temperature and near-ambient-pressure environments
BibTeX
@article{danikas2026temperature,
title = {{Temperature and Pressure Effects on the Dynamics of Elastomeric Dioxaborolane Vitrimers}},
author = {Michail Danikas and Matteo Conti and Johan Mattsson and Nathan J van Zee and Renaud Nicolaÿ and Laurence Ramos and George Floudas},
journal = {Macromolecules},
year = {2026},
month = sep,
doi = {10.1021/acs.macromol.6c01360},
url = {https://hal.science/hal-05797777v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Temperature and Pressure Effects on the Dynamics of Elastomeric Dioxaborolane Vitrimers
AU - Michail Danikas
AU - Matteo Conti
AU - Johan Mattsson
AU - Nathan J van Zee
AU - Renaud Nicolaÿ
AU - Laurence Ramos
AU - George Floudas
PY - 2026
DA - 2026/09/05
JO - Macromolecules
DO - 10.1021/acs.macromol.6c01360
UR - https://hal.science/hal-05797777v1
AB - We report the synthesis, and the thermal, viscoelastic and dynamic properties of a series of dioxaborolane-based poly(n-butyl methacrylate) (PBMA) vitrimers, as a function of molar mass and cross-linking density. By combining calorimetry, dielectric spectroscopy and rheology, we explored the different characteristic temperatures that influence the dynamics of vitrimers. Three main processes could be identified by dielectric spectroscopy, the local β-process, the segmental α-process and the merged αβ-process at higher temperatures. Pressure was employed to examine their sensitivity through an apparent activation volume. We found that the local β-process was only weakly affected by pressure, and that the rubber-to-glass temperature continuously increased with vitrimer cross-linking density. Our results revealed that the dynamic bonds in vitrimers contribute to an effective unit of relaxation (e.g. an effective segment) that is larger than that in the corresponding homopolymer. In addition, the ratio of activation energies at constant volume and at constant pressure revealed that the segmental dynamics in the vitrimers is controlled by intra-molecular barriers. The viscoelastic properties are influenced by the topology freezing temperature, TV, separating segmental-controlled dynamics at lower temperatures from the bond exchange mechanism at higher temperatures initiating the flow. The derivative approach applied to the viscoelastic shift factors was found to be a practical method to locate TV. In the vitrimers, the bond exchange mechanism had a high apparent activation energy (E ∼ 90 kJ/mol) similar to that of the segmental dynamics. We present the first high-pressure investigation of the relaxation dynamics in vitrimers, elucidating the origin of the segmental process and re-defining the fundamental effective unit of relaxation.
SN - 0024-9297
SN - 1520-5835
ER -