Length Effect of Crosslinkers on the Mechanical Properties and Dimensional Stability of Vitrimer Elastomers with Inhomogeneous Networks

Inhomogeneous network construction is a useful strategy to solve the trade-off between mechanical strength and creep in vitrimer rubbers. But it is still lack of tools to tune the mechanical properties and network dynamics of this new system. In this paper, uneven distribution of functional groups was realized by sequential coordination polymerization of myrcene and isoprene and epoxidation. The following epoxidation and curing generated VMI-x samples with inhomogeneous network. Polyisoprene was used to prepare control samples called VPI-x with homogeneous network. Different lengths of dicarboxylic acid crosslinkers (SA = succinic acid, HA = heptanedioic acid, DA = decanedioic acid) were used to probe their effects on dynamic behaviors, mechanical properties and recyclability. Morphological test and nanomechanical mapping confirmed the inhomogeneous feature of VMI-x samples. For both inhomogeneous and homogeneous samples, SA and DA crosslinkers brought higher tensile strength and modulus, earlier SIC phenomenon and higher orientation percentage of amorphous molecular chains than those of HA, which are ascribed to extra permanent cross-linking existing in SA samples and transition entanglements existing in DA samples. However, the constrain effect of SA crosslinker is too strong in inhomogeneous network to sacrifice the extensibility, which is much smaller than those of HA and DA. SA and DA samples also present restricted segmental motion and superior creep resistant properties compared to HA samples according to the results of broadband dielectric spectroscopy and DMA test. Differently, at high temperature above 130 degrees C, the stress relaxation, topology freezing transition temperature (Tv) and recycling efficiency of strength are dominated by the crosslinker length monotonically, probably due to the disentanglement of DA crosslinkers. Compared to homogeneous network, inhomoge-neous ones showed obvious enhanced mechanical properties, lower hysteresis, quicker segmental relaxation, lower creep and quicker network relaxation. This work demonstrates that crosslinker lengths could tune the vast aspects of vitrimer elastomers and is a non-negligible factor to determine their properties, especially for those with inhomogeneous networks.