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In this work, three types of agricultural waste: olive stones (OS), date seed (DS) and wheat bran (WB) were applied as potential lignocellulosic fillers in poly(ε-caprolactone) (PCL) based biocomposites. Differences in composites' performance were related to the higher content of proteins, noted for WB comparing to other fillers applied, which enhanced plasticization of PCL matrix. The mechanical properties of biocomposites were significantly affected by the agricultural waste fillers. Use of WB caused an obvious, even 25% decrease of tensile strength and hardness, which could be explained on account of glass transition temperature depletion and weaker matrix-filler interfacial interactions. Such phenomenon also increased water uptake of PCL/WB composites by more than 100%, while for PCL/OS and PCL/DS systems only for about 50%. Thermogravimetric analysis revealed that all investigated composites can be effectively processed without thermal decomposition. Generally, the outcome of this work demonstrated that OS, DS, and WB could be applied as promising lignocellulosic fillers used in manufacturing of high-performance polymer biocomposites.

The synthesis and characterization of polyethylene−polyester block and graft copolymers and their potential as compatibilizers in polyethylene-based polymer blends are being described. The various routes to functionalized polyethylenes and the corresponding block/graft copolymers have been compared and evaluated for their scalability to industrial scale production. Hydroxyl chain-end and randomly OH-functionalized HDPE as well as randomly OH-functionalized LLDPE were employed as macroinitiators for producing the corresponding block and graft copolymers. These materials were prepared using two different strategies. The graf ting f rom approach entails catalytic ring-opening polymerization of lactones, i.e., ε-caprolactone and ω-pentadecalactone and hydroxyl-functionalized polyethylenes as macroinitiator. The alternative graf ting onto approach involves the preparation of block and graft copolymers via simple and convenient transesterification of polycaprolactone or polypentadecalactone with OH-functionalized polyethylenes. The copolymers were characterized in terms of their molecular weight (SEC), chemical structure (liquid state NMR), topology (MALDI-ToF-MS), supramolecular assembly (solid state NMR), and thermal properties (DSC analysis). The applied techniques for synthesizing the copolymers allow preparation of the products with sufficiently high molecular weight of the final materials. The copolymers were tested as compatibilizers for polyethylene/polycarbonate blends. As proven by SEM analysis, addition of the compatibilizers resulted in a significant improvement of the blend morphology.

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The modification of poly(ε-caprolactone) (PCL) was successfully conducted during reactive processing in the presence of dicumyl peroxide (DCP) or di-(2-tert-butyl-peroxyisopropyl)-benzene (BIB). The peroxide initiators were applied in the various amounts of 0.5 or 1.0 pbw (part by weight) into the PCL matrix. The effects of the initiator type and its concentration on the structure and mechanical and thermal properties of PCL were investigated. To achieve a detailed and proper explication of this phenomenon, the decomposition and melting temperatures of DCP and BIB initiators were measured by differential scanning calorimetry. The conjecture of the branching or cross-linking of PCL structure via used peroxides was studied by gel fraction content measurement. Modification in the presence of BIB in PCL was found to effectively increase gel fraction. The result showed that the cross-linking of PCL started at a low content of BIB, while PCL modified by high DCP content was only partially cross-linked or branched. PCL branching and cross-linking were found to have a significant impact on the mechanical properties of PCL. However, the effect of used initiators on poly(ε-caprolactone) properties strongly depended on their structure and content. The obtained results indicated that, for the modification towards cross-linking/branching of PCL structure by using organic peroxides, the best mechanical properties were achieved for PCL modified by 0.5 pbw BIB or 1.0 pbw DCP, while the PCL modified by 1.0 pbw BIB possessed poor mechanical properties, as it was related to over cross-linking.