Entropic phase separation in polymer--vitrimer melts

Fuente: arXiv
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Main Authors: Constantinou, A. A. Rispo, Magyari, B., Ianniruberto, G., van Ruymbeke, E., Read, D. J.
Format: Preprint
Published: 2026
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_version_ 1866918411172315136
author Constantinou, A. A. Rispo
Magyari, B.
Ianniruberto, G.
van Ruymbeke, E.
Read, D. J.
author_facet Constantinou, A. A. Rispo
Magyari, B.
Ianniruberto, G.
van Ruymbeke, E.
Read, D. J.
contents Traditional plastics demand a choice between durability (thermosets) and reprocessability (thermoplastics). Vitrimers are a recent class of polymer network combining both these qualities. Their increased cost of production can be offset by mixing them with a traditional thermoplastic; however, phase separation in such blends can lead to inhomogenous materials. In this paper, we adapt an existing model for the free energy of dissociative polymer networks to their associative, vitrimeric counterpart. We test the accuracy of the model's predictions by comparing them with the results of novel molecular-dynamics simulations. We demonstrate that such melts can undergo phase separation even in the absence of energetic interactions between the components. We find furthermore that the phase diagram of the melts is qualitatively similar to that of dissociative systems, and that the critical degree of conversion for the onset of phase separation depends reciprocally on the number of function sites per vitrimer chain.
format Preprint
id arxiv_https___arxiv_org_abs_2603_25532
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Entropic phase separation in polymer--vitrimer melts
Constantinou, A. A. Rispo
Magyari, B.
Ianniruberto, G.
van Ruymbeke, E.
Read, D. J.
Soft Condensed Matter
Traditional plastics demand a choice between durability (thermosets) and reprocessability (thermoplastics). Vitrimers are a recent class of polymer network combining both these qualities. Their increased cost of production can be offset by mixing them with a traditional thermoplastic; however, phase separation in such blends can lead to inhomogenous materials. In this paper, we adapt an existing model for the free energy of dissociative polymer networks to their associative, vitrimeric counterpart. We test the accuracy of the model's predictions by comparing them with the results of novel molecular-dynamics simulations. We demonstrate that such melts can undergo phase separation even in the absence of energetic interactions between the components. We find furthermore that the phase diagram of the melts is qualitatively similar to that of dissociative systems, and that the critical degree of conversion for the onset of phase separation depends reciprocally on the number of function sites per vitrimer chain.
title Entropic phase separation in polymer--vitrimer melts
topic Soft Condensed Matter
url https://arxiv.org/abs/2603.25532