The degradation pattern of bacterial poly-3-hydroxybutyrate (PHB) in dimethylformamide (DMF) and dioxane solutions at 100 °C assisted by ethylenediamine, 1,4-diaminobutane and monoaminoethanol was studied. When diamines were introduced into the PHB solution in DMF in the amount of 1 mol of the reagent to 5 or 10 mol of PHB monomers, a rapid decrease in the molecular weight of the polymer was observed. The initial value of the weight average molecular weight (Mw) 840 kDa had decreased by 20–30 times within the first 10–20 min of the experiment, followed by its gradual decrease to several thousand Da. When a similar molar quantity of aminoethanol was added, the molecular weight decreased slower. PHB had been degrading much slower in the dioxane solution than in DMF. By varying the number of reagents, it was possible to reach stabilization of the Mw at 1000–3000 Da when using diamines and 8000–20,000 Da using aminoethanol. 1H NMR analysis of the oligomers revealed of amino and amido groups forming in their structure. From the opposite end of the polymer chain, residues of 3-hydroxybutyric, crotonic and isocrotonic acids were formed during degradation. Differential scanning calorimetry indicated that after oligomerization there was a decrease in the melting point from 178 °C to 140–170 °C depending on the decrease in the molecular weight. The method proposed can be used for obtaining aminated PHB oligomers.
Eco-friendly polymer composites in the form of granules based on biodegradable polycaprolactone (PCL) with the inclusion of montmorillonite (MMT) from 5 to 50 wt% were prepared by solution-casting and melt extrusion. The physicochemical properties of the composite granules were studied using FTIR spectroscopy, XRDA, DSC, and TGA methods. The paper presents comparative values of crystallinity of composite granules which depend on the method of measuring (XRDA, DSC). It was shown that the crystallinity of PCL/MMT granules was affected by the preparation method and by the MMT content, and that with increase in MMT content, crystallinity increased by up to 61–67%. The change in crystallinity of the granules also affected its biodegradation in soil. At the end of exposure in soil, the mass loss for the granules prepared by solution-casting was more than 90%, whereas for the composite granules prepared by extrusion it was less than 60%. Applying melt extrusion enabled obtaining intercalated composites with predictable features, whereas only mixed-structure microcomposites could be prepared by solution-casting.
The need for a long-term sustaining of optimal concentrations of applied pesticides in the soil in agriculture resulted in the development of systems for controlled release of active substances. Such systems are based on the use of eco-friendly carrier materials that are harmless to plants, humans and environment. Inorganic substances (e.g., clays or alike substances), biodegradable polymers of natural or synthetic origin, blends of such polymers and their composites with inorganic fillers can be used as carriers. The deposited pesticides are released by diffusion or, in the case of systems based on biodegradable polymers, by degradation of the carrier. Inorganic carriers are usually impregnated with a pesticide. As for polymers, there is a wide range of methods for obtaining forms. Namely, these are the microsphere and nanoparticle formation, film casting, tablet pressing, form gelatinizing, and coprecipitation of a pesticide and a polymer from a solution. Co-extrusion of pesticides with polymers or their composites at temperatures below the degradation temperature of the components is another promising method for obtaining pesticide carriers.
In this study the effect of processing methods on physical and chemical properties of polylactide (PLA) (Mn 130 kDa, L-93/ D-7) was investigated. PLA-films were obtained by solution casting and melt extrusion using Bestfiilament extruder equipped with flat-slot die. SEM, AFM, FTIR-spectroscopy and DSC were used for characterization of the films. The films obtained by flat-slot die melt extrusion had a relief surface with prominent strands and inclusions, while the cast films had a smooth surface with pores or gaps ranging in size from 20 to 60 μm. The average roughness (Ra) and root-mean-square roughness (Rq) of the surface of cast films were at the level of 45-48 and 37-39 nm, respectively. Meanwhile, for the melt films these values increased and corresponded to 122 and 65 nm, respectively. According to FTIR, both types of films were characterized by an increase in the absorption peaks at 1800-1700, 1450-1470 and 1350-1320 cm-1, which correspond to stretch vibrations of ester bond and bending vibrations of the C-H bond, respectively. DSC data showed decrease in crystallinity of PLA and change in its internal structure from amorphous-crystalline to amorphous after the processing.
To find out whether Al2O3 nanofiller is effective in improving the characteristics of polymer composites, composite polymer films based on biodegradable polylactide and epoxidized aluminum oxide nanofibers were obtained by solution casting. Surface morphology, mechanical and thermal properties of composites were studied by SEM, IR-Fourier spectroscopy, DSC and DMA. It was shown that, below and above the percolation threshold, the properties of the films differ significantly. The inclusion of alumina nanoparticles up to 0.2% leads to a plasticizing effect, a decrease in the crystallization temperature and the melting enthalpy and an increase in the tensile stress. An increase in the content of alumina nanoparticles in films above the percolation threshold (0.5%) leads to a decrease in the crystallinity of the films, an increase in stiffness and a drop in elasticity. Finding the percolation threshold of alumina nanoparticles in PLA films makes it possible to control their properties and create materials for various applications. The results of this study may have major significance for the commercial use of aluminum oxide nanofibers and can broaden the research field of composites.