In our current paper the preparation and properties of thermoplastic elastomer produced by dynamic vulcanization is presented and discussed. We dynamically vulcanized natural and styrene butadiene rubber (NR/SBR) phase by continuous extrusion. Dispersion and in-situ vulcanization of the rubber phase occurred simultaneously in a co-rotating twin screw extruder. We used a random polypropylene copolymer (rPP) as the thermoplastic matrix and untreated crumb rubber (CR) to partially substitute the neat fresh rubber in order to check whether this is a potential recycling route for waste rubber products. We studied the effect of various rubber formulations, various processing conditions (screw speed and configuration) and various CR particle size distributions by characterizing the mechanical performance of the thermoplastic dynamic vulcanizates (TDVs) with tensile and hardness tests and their morphology by evaluating SEM micrographs taken from the fracture surfaces of the tensile specimens. The results showed that increasing screw speed and more high-shear elements in the screw setup led to a finer dispersion of the rubber phase, resulting in improved mechanical properties. The ultimate tensile properties of the best TDVs reached 20.5 MPa in tensile strength and 550 % in strain at break. However, partial replacement of the fresh rubber with untreated CR caused a significant deterioration in mechanical properties, due to poor adhesion between the CR particles and the matrix and rubber. This suggests that some kind of pre-treatment (e.g. by microwave or other devulcanization techniques) is necessary to enhance the surface activity of the CR particles.
The aim of this paper was the detailed investigation of the properties of one-shot bulk polymerized thermoplastic polyurethanes (TPUs) produced with different processing temperatures and the properties of thermoplastic dynamic vulcanizates (TDVs) made by utilizing such in situ synthetized TPUs as their matrix polymer. We combined TPUs and conventional crosslinked rubbers in order to create TDVs by dynamic vulcanization in an internal mixer. The rubber phase was based on three different rubber types: acrylonitrile butadiene rubber (NBR), carboxylated acrylonitrile butadiene rubber (XNBR), and epoxidized natural rubber (ENR). Our goal was to investigate the effect of different processing conditions and material combinations on the properties of the resulting TDVs with the opportunity of improving the interfacial connection between the two phases by chemically bonding the crosslinked rubber phase to the TPU matrix. Therefore, the matrix TPU was synthesized in situ during compounding from diisocyanate, diol, and polyol in parallel with the dynamic vulcanization of the rubber mixture. The mechanical properties were examined by tensile and dynamical mechanical analysis (DMTA) tests. The morphology of the resulting TDVs was studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM) and the thermal properties by differential scanning calorimetry (DSC). Based on these results, the initial temperature of 125 °C is the most suitable for the production of TDVs. Based on the atomic force micrographs, it can be assumed that phase separation occurred in the TPU matrix and we managed to evenly distribute the rubber phase in the TDVs. However, based on the SEM images, these dispersed rubber particles tended to agglomerate and form a quasi-continuous secondary phase where rubber particles were held together by secondary forces (dipole–dipole and hydrogen bonding) and can be broken up reversibly by heat and/or shear. In terms of mechanical properties, the TDVs we produced are on a par with commercially available TDVs with similar hardness.
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