Vitrimer
materials that obscure the line between ″thermoset″
and ″thermoplastic″ have already attracted a great deal
of interest since they exhibit dynamic properties of stress relaxation
or reprocessability without losing their permanently cross-linked
networks. While much research has been aimed at developing new exchangeable
dynamic bonds to broaden the scope, there is a dearth of effort in
exploring the key factors that influence the dynamic properties of
vitrimer materials. These explorations are not only useful in the
exact design and synthesis of vitrimer materials but also quite important
in their theory establishment and computer simulation. However, only
a few ways including catalyst control have been confirmed to be the
key factors in controlling the dynamic properties of classical vitrimer
materials like the polyester-based epoxy vitrimer. Here, we proposed
that the density of exchangeable ester bonds (υ) in networks
also has a crucial role in adjusting the dynamic properties of epoxy
vitrimers. Four polyester-based epoxy vitrimers were synthesized from
the tricarboxylic acid curing agent and different epoxy monomers,
resulting in various υ’s. These epoxy vitrimers were
named ″E202-vitrimer″, ″E380-vitrimer″, ″E500-vitrimer″, and
″E640-vitrimer″ according to the different
molecular weights of the epoxy monomer. It was revealed that the dynamic
properties of these vitrimer materials varied with the υ value.
From the E640-vitrimer to E202-vitrimer, the
stress relaxation behavior sped up with the rise in υ and the
characterized relaxation times (τ’s) obviously decreased.
Meanwhile, the activation energy (E
a)
and the Arrhenius prefactor (τ0), which are two important
intrinsic parameters in evaluating the dynamic properties of vitrimers,
exhibited heavy dependence on υ, while linear models were applied
to describe their relationships. Moreover, the τ at various
temperatures could be also predicted from a linear model that relied
on the υ in polyester vitrimers. These results indicated that
υ has a crucial role in controlling the dynamic properties of
polyester-based epoxy vitrimers and the value of υ could be
applied to calculate the τ, E
a,
and τ0. Besides, the influence of υ on the
dynamic properties of polyester-based epoxy vitrimers and the resulted
models might be workable in other vitrimer materials, which can be
utilized to design desired vitrimer materials for various applications.
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