For both environmental and economic reasons, there is broad interest in recycling rubber and in the continued development of recycling technologies. The use of postindustrial materials is a fairly well-established and documented business. Much effort over the past decade has been put into dealing with of end-of-life tires from landfills and vacant fields. It is only in the last few years that more business opportunities for recycled rubber have come to the forefront. Reclaiming rubber has gained increasing interest, more so in Europe than in North America. In those areas, much work has been done to refine the processes used. The major form of recycled rubber is still ground rubber. This is produced either by cryogenic, ambient, or wet grinding. The material is then used neat with sulfur/curatives, binders, or cements. The binders are normally moisture curable urethanes, liquid polybutadienes, or latex to produce items such as mats, floor tiles, and carpet undercushion. Recycled rubber is still used as tire derived fuel, but less so than 10 years ago. Another outlet is as an additive to asphalt. Recycled rubber can be used in the plastics industry, for which much development is being done. Large particle size ground rubber or chips are used in civil engineering applications, landscaping, or artificial turf. In terms of applications, most use is outside of the conventional rubber industry. Cost factors are still addressed in the tire industry. As of 2012, approximately 8–10% recycled material is used in tires. The biggest obstacles to further adaption are safety factors and property loss. Better methods are needed for treating or modifying the rubber surface and for regenerating the rubber through devulcanization. Devulcanization gives the highest quality recycled material in terms of processing and properties. However, shortcomings to devulcanization are reduced process safety and odorous chemicals that are required at present.

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The optimal process conditions for a high ratio of devulcanization to polymer degradation have been investigated for tire rubbers: styrene–butadiene rubber (SBR), butadiene rubber (BR), natural rubber (NR), and chloro-isobutylene–isoprene rubber (CIIR). These polymers all show their own particular breakdown characteristics. The temperature dependence of the breakdown mechanism was investigated by measuring sol fractions and cross-link densities. For SBR and BR, the highest reduction in cross-link density was found at a temperature of 220 °C, together with a moderate increase in sol content. According to the Horikx theory, which correlates sol fraction and a decrease in cross-link density, this is the result of a high degree of cross-link scission. Higher process temperatures result in a lower decrease in cross-link density due to recombination of active chain fragments. NR and CIIR show different behavior. Breakdown of NR in this temperature range results in an almost complete destruction of the polymer network; cross-link density is reduced to almost zero, and the sol fraction is close to 100%. The same result is found for CIIR at higher temperatures. Although different rubbers react via other devulcanization mechanisms, the best devulcanization conditions for whole passenger car tire material are optimized.

Maleated natural rubber (MNR) was prepared and used to formulate thermoplastic vulcanizates (TPVs) based on various MNR/PP blends. The influence of mixing methods on the TPVs properties was first studied. We found that mixing all ingredients in an internal mixer provided the TPVs with better mechanical properties. The final mixing torque, shear stress, and shear viscosity of the TPVs prepared with various blend ratios of MNR/PP increased with increasing levels of MNR in the blends. This may be attributed to higher shear viscosity of the pure MNR than that of the pure PP. Furthermore, as evidenced in SEM micrographs, the TPVs are two phase morphologies with dispersed small vulcanized rubber domains in the PP matrix. Therefore, the higher content of PP caused the more molten continuous phase of the flow during mixing and rheological characterization. Tensile strength and hardness of the TPVs increased with increasing levels of PP, while the elongation at break decreased. Furthermore, the elastomeric properties, in terms of tension set, increased with increasing levels of MNR in the blends. This may be attributed to decreasing trends in the size of vulcanized rubber particles dispersed in the PP matrix with an increasing concentration of MNR. POLYM. ENG. SCI. 46:594–600, 2006. © 2006 Society of Plastics Engineers.

Abstract:As a means to decrease the amount of waste tires and to re-use tire rubber for new tires, devulcanization of ground passenger car tires is a promising process. Being an established process for NR and EPDM, earlier work has shown that for ground passenger car tire rubber with a relatively high amount of SBR, a devulcanization process can be formulated, as well. This was proven for a laboratory-scale batch process in an internal mixer, using diphenyl disulfide as the devulcanization aid and powder-sized material. In this paper, the devulcanization process for passenger car tire rubber is upscaled from 15 g per batch and transformed into a continuous process in a co-rotating twin screw extruder with a capacity of 2 kg/h. As SBR is rather sensitive to devulcanization process conditions, such as thermal and mechanical energy input, the screw design was based on a low shear concept. A granulate with particle sizes from 1-3.5 mm was chosen for purity, as well as economic reasons. The devulcanization process conditions were fine-tuned in terms of: devulcanization conditions (time/temperature profile, concentration of devulcanization aid), extruder parameters (screw configuration, screw speed, fill factor) and ancillary equipment (pre-treatment, extrudate handling). The influence of these parameters on the devulcanization efficiency and the quality of the final product will be discussed. The ratio of random to crosslink scission as determined by a Horikx plot was taken for the evaluation of the process and material. A best practice for continuous devulcanization will be given.

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