Processing Stabilization of Polyethylene with Grape Peel Extract: Effect of Extraction Technology and Composition.

Dry grape peel powder was extracted by three different techniques, stirred tank reactor, Soxhlet and ultrasound extraction. The composition, physical and chemical structure and inherent stability of the extracts were characterized by various methods. The extracts and reference compounds were added to polyethylene and their stabilization efficiency was determined in multiple extrusion experiments. The composition of the extracts was quite similar. Ten main compounds were identified in the extracts, which contained a considerable number of polyphenols, but only small amounts of quercetin and trans-resveratrol. The extracts proved to be more efficient processing stabilizers than trans-resveratrol and the commercial stabilizer, Irganox 1010, irrespective of the extraction technology used. In spite of their good processing stabilization effect, polymers containing the extracts had poor residual stability. The differences in processing and long-term stabilization must be related to the different structures of the polyphenols contained by the extracts and the reference compounds. The results clearly prove that the IC50 value determined by the DPPH assay is not suitable for the estimation of the efficiency of a compound as a stabilizer for polymers.

Effect of competitive interactions on the structure and properties of blends prepared from an industrial lignosulfonate polymer.

To explore the possibility of applying lignin in practice, an industrial lignosulfonate (0-50 vol%) was blended with four ionomers. The concentrations of carboxyl and carboxylate groups were systematically varied in the ethylene-acrylic acid copolymers to study the competition of hydrogen and ionic bonds forming between the components. The mechanical properties of the blends were determined by tensile testing. The structure was investigated by scanning electron microscopy, while deformation and failure processes were studied by acoustic emission measurements and microscopy. Interfacial interactions were quantitatively characterized by analyzing local deformation processes and by evaluating the composition dependence of the tensile strength using appropriate models. Molecular dynamics simulations indicated that carboxylate groups preferably form clusters in the ionomer phase, consequently, the increasing degree of neutralization results in ionomers with more and more self-interactions of components deteriorating ionomer-lignin interactions. The novel combination of experiments, modeling, and simulation was done for the first time on such materials, and it pointed out that the role of hydrogen bonds is more critical in determining blend properties. Blends can be prepared for practical applications with a good combination of stiffness (0.8 GPa), tensile strength (22 MPa), and elongation-at-break (25 %) at 30 vol% lignosulfonate content and 33 % neutralization.

Interactions, Structure and Properties of PLA/lignin/PBAT Hybrid Blends.

Poly(butylene adipate-co-terephthalate) (PBAT) was added to poly(lactic acid) (PLA)/lignin blends to decrease the considerable stiffness and brittleness of the blends. Two- and three-component blends were prepared in a wide composition range through homogenization in an internal mixer followed by compression molding. Interactions among the components were estimated by comparing the solubility parameters of the materials used and through thermal analysis. Mechanical properties were characterized by tensile testing. The structure of the blends was studied using scanning electron (SEM) and digital optical (DOM) microscopy. The results showed that the interactions between PBAT and lignin are somewhat stronger than those between PLA and the other two components. The maleic anhydride grafted PLA added as a coupling agent proved completely ineffective; it does not modify the interactions. The structural analysis confirmed the immiscibility of the components; the structure of the blends was heterogeneous at each composition. A dispersed structure formed when the concentration of one of the components was small, while, depending on lignin content, an interpenetrating network-like structure developed and phase inversion took place in the range of 30-60 vol% PBAT content. Lignin was located mainly in the PBAT phase. Properties were determined by the relative amount of PBAT and PLA; the addition of lignin deteriorated properties, mainly the deformability of the blends. Other means, such as reactive processing, must be used to improve compatibility and blend properties. The results contribute considerably to a better understanding of structure-property correlations in lignin-based hybrid blends.

Stabilization of PE with Pomegranate Extract: Contradictions and Possible Mechanisms.

Dry pomegranate peel was extracted with acetone and the extract was added to a Phillips type polyethylene. The concentration of the extract was changed from 0 to 1000 ppm in six steps and stabilization efficiency was checked by the multiple extrusion of the polymer followed by the characterization of chemical structure, processing, and residual stability. The results confirmed the excellent processing stabilization efficiency of the extract, but also the poor long-term stability of PE containing it in accordance with previously published results. The extract is amorphous and its solubility is relatively large in the polymer; thus, these factors cannot be the reason for the poor stabilization efficiency in an oxygen-rich environment. Chemical factors like the self-interaction of the polyphenol molecules, the stability of the radicals forming after hydrogen abstraction, and the lack of hydrogens with the necessary reactivity must be considered during the evaluation of the efficiency of the extract. These factors as well as the insufficient number of active hydrogens hinder the reaction of the additive molecules with oxygen-centered radicals, thus leading to inferior long-term stability. The extract can be used for the processing stabilization of polymers, but for applications requiring long-term stability, it must be combined with other natural antioxidants like flavonoids or Vitamin E.