Using the method of pyrolytic mass spectrometry in the study of biodegradable polymeric materials

The results of pyrolytic mass spectrometry studies of biodegradable polymeric materials based on polyolefins and segmented polyurethanes with various functional additives are summarized. The structure and composition of initial and after exposure in soil, climate chamber and after exposure to microorganisms (bacteria, yeast) composites are characterized. In the research presented, influence of acetates and complexonates of metals, including cobalt, copper and zinc, on the structural changes in the high pressure polyethylene (HPPE) occurring under the impact of factors such as temperature, humidity and UV-radiation is investigated. It was established, that samples of HPPE, modified by cobalt acetate and cobalt and copper complexonates are responsive and most sensitive to the action of above-mentioned physical factors. Investigation of a segmented polyurethanes (SPU) of a different chemical structure influenced by a factors, modeling of the environmental conditions was conducted. It was shown using pyrolytic mass-spectrometry method and monitoring of samples’ weight loss that under the influence of above-mentioned environmental factors in the SPU occurs processes, resulting to changing its micro heterogeneous structure. It is established that SPU having ester links in its structure and being exposured in soil for 120 days is predominantly attacked by microorganisms, then the main active factor appears to be soil’ pH value – after 300 days in soil with alkaline or acid solution SPU sample decomposes into a separate fragments. Features of the chemical structure of urethane polymers synthesized on the base of hydroxylated rapeseed oil (polyol) were examined. Analysis of the results showed that the macromolecular compounds obtained are segmented polyurethanes which thermal degradation occurs in two stages: hard blocks are destroyed at the first stage, while polyol part (soft blocks) decomposes at the second stage, allowing to identify the temperature area of polymer destruction and thus its temperature region of operation. It is shown that the most suitable from the viewpoint of environmental friendly is polyurethane composition containing more than 50% of polyol. Thermal mass-spectrometry (TMS) has been employed to investigate processes of thermal destruction of segmented polyurethane and it’s compositions filled by polysaccharides: starch, dextrin, chitosan. The features of thermal destruction for segmented polyurethane and related compositions before and after their storage in a soil have been determined. Application TMS is shown to permit the processes of biodegradation of polymeric materials to investigate.

Design and Synthesis of Bio-Inspired Polyurethane Films with High Performance

In the present work, the synthesis of segmented polyurethanes functionalized with catechol moieties within the hard or the soft segment is presented. For this purpose, a synthetic route of a new catechol diol was designed. The direct insertion of this catechol-free derivative into the rigid phase led to segmented polyurethanes with low performance (σmax ≈ 4.5 MPa). Nevertheless, when the derivative was formally located within the soft segment, the mechanical properties of the corresponding functionalized polyurethane improved considerably (σmax ≈ 16.3 MPa), owing to a significant increase in the degree of polymerization. It is proposed that this difference in reactivity could probably be attributed to a hampering effect of this catecholic ring during the polyaddition reaction. To corroborate this hypothesis, a protection of the aromatic ring was carried out, blocking the hampering effect and avoiding secondary reactions. The polyurethane bearing the protected catechol showed the highest molecular weight and the highest stress at break described to date (σmax ≈ 66.1 MPa) for these kind of catechol-functionalized polyurethanes. Therefore, this new approach allows for the obtention of high-performance polyurethane films and can be applied in different sectors, benefiting from the molecular adhesion introduced by the catechol ring.

Block Copolymers of Poly(ω-Pentadecalactone) in Segmented Polyurethanes: Novel Biodegradable Shape Memory Polyurethanes

In this report, the synthesis of poly(ω-pentadecalactone) (PPDL) (co)polymers and their incorporation into polyurethanes (PUs) are reported. Optimal conditions for the ring-opening polymerization (ROP) of ω-pentadecalactone (PDL) using dibutyltin dilaurate catalyst were established. For the synthesis of linear and crosslinked PUs, 50 kDa poly(ε-caprolactone) (PCL) and 1,6-hexamethylenediisocyanate (HDI) were used. The obtained polyurethanes were characterized by Attenuated Total Reflectance Fourier-Transform Infrared spectroscopy (AT-FTIR), differential scanning calorimetry (DSC), and dynamical mechanical analysis (DMA). The DMA of the selected sample showed a rubbery plateau on the storage modulus versus temperature curve predicting shape memory behavior. Indeed, good shape memory performances were obtained with shape fixity (Rf) and shape recovery (Rr) ratios.