Halogen-free flame-retardant compounds. Thermal decomposition and flammability behavior for alternative polyethylene grades

The effect of six halogen-free flame retardant (FR) formulations was investigated on the thermal stability of two low-density polyethylenes (LDPE) and one linear low-density polyethylene (LLDPE), by means of thermogravimetric analysis (TGA) under nitrogen and air atmosphere. The relative data were combined with flammability properties and the overall performance of the FRs was correlated with the type of branching in the polyethylene grades and to their processing behavior. The thermal degradation kinetics was further determined based on the Kissinger and Coats-Redfern methods. In terms of flammability, the addition of a triazine derivative and ammonium polyphosphate at a loading of 35 wt. %. was found to be the most efficient, leading to UL 94 V0 ranking in the case of the LDPE grade produced in an autoclave reactor. - 2019 by the authors.Funding: This publication was made possible by the NPRP award [NPRP 9-161-1-030] from the Qatar National Research Fund (a member of The Qatar Foundation). The statements made herein are solely the responsibility of the author(s)

Enhancing the UV/heat stability of LLDPE irrigation pipes via different stabilizer formulations

Herein different stabilizer formulations of linear low-density polyethylene (LLDPE) against UV- and heat-initiated degradation are described. The project aims at outdoor applications, such as irrigation piping and profiles, in the Middle East desert regions, where long-term weathering stability due to high temperatures and solar radiation is important. Two UV/heat formulations, without and with carbon black (CB) as pigment, were incorporated into LLDPE by melt compounding. Neat LLDPE and the stabilized compounds were exposed to accelerated UV and heat aging. Morphological analysis through scanning electron microscopy of the UV-exposed neat LLDPE showed more severe surface cracking compared to the CB-containing LLDPE, while all stabilized compounds did not show any surface degradation. Crack formation was less visible for the thermally aged samples. A significant decrease in molecular weight (MW) was observed for the neat UV-exposed LLDPE, while both unpigmented stabilized compounds showed little change in MW. Mechanical properties, thermal analysis, and carbonyl index results supported the morphological results, which confirmed that CB alone was slightly more effective in protecting the LLDPE against UV initiated degradation, but performed worse against thermal initiated degradation. UV1 and UV2 compounds were efficient against both UV- and heat-initiated degradation, with UV1 performing better for unpigmented compounds, and UV2 for the pigmented ones.This publication was made possible by the NPRP award (NPRP 9-161-1-030) from the Qatar National Research Fund (a member of The Qatar Foundation). We are also grateful to BASF and Sabo for supplying the additives at no cost. We further express our gratitude to Dr. Robert Brüll from Fraunhofer LBF, Darmstadt, Germany for doing the GPC analyses on our samples. The statements made herein are solely the responsibility of the author(s).Scopu

Green Pathways for the Enzymatic Synthesis of Furan-Based Polyesters and Polyamides

The attention towards the utilization of sustainable feedstocks for polymer synthesis has grown exponentially in recent years. One of the spotlighted monomers derived from renewable resources is 2,5-furandicarboxylic acid (FDCA), one of the most promising bio-based monomers, due to its resemblance to petroleum-based terephthalic acid. Very interesting synthetic routes using this monomer have been reported in the last two decades. Combining the use of bio-based monomers and non-toxic chemicals via enzymatic polymerizations can lead to a robust and favorable approach towards a greener technology of bio-based polymer production. In this chapter, a brief introduction to FDCA-based monomers and enzymatic polymerizations is given, particularly focusing on furan-based polymers and their polymerization. In addition, an outline of the recent developments in the field of enzymatic polymerizations is discussed. </p

Encapsulation of oregano (Origanum onites l.) essential oil in β-cyclodextrin (β-CD): Synthesis and characterization of the inclusion complexes

The aim of the present work was to study the encapsulation of Origanum onites L. essential oil (oregano EO) in β-cyclodextrin (β-CD) inclusion complexes (ICs), using the co-precipitation method. The formed β-CD–oregano EO ICs were characterized by diverse methods, such as Dynamic Light Scattering (DLS), FT-IR spectroscopy, Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Nuclear Magnetic Resonance (NMR) spectroscopy and Scanning Electron Microscopy (SEM). UV-Vis spectroscopy was used for the determination of the inclusion efficacy and the study of the encapsulated oregano EO release profile. The interactions between host (β-CD) and guest (oregano EO) in the formed ICs were proven by the FT-IR, DSC, TG and NMR analyses. The ICs, which derived from different batches, presented nanoscale size (531.8 ± 7.7 nm and 450.3 ± 11.5 nm, respectively), good size dispersion (0.308 ± 0.062 and 0.484 ± 0.029, respectively) and satisfactory stability in suspension (ζ-potential = −21.5 ± 1.2 mV and −30.7 ± 1.8 mV). Inclusion efficiency reached up to 26%, whereas the oregano EO release from the ICs followed a continuous delivery profile for up to 11 days, based on in vitro experiments. The formed ICs can find diverse applications, such as in the preparation of films for active packaging of food products, in personal care products for the improvement of their properties (e.g., antioxidant, antimicrobial, etc.), as well as in insect repellent products. © 2017 by the authors. Licensee MDPI, Basel, Switzerland

Accelerated ageing and hydrolytic stabilization of poly(lactic acid) (PLA) under humidity and temperature conditioning

The accelerated hygrothermal ageing of two commercial poly(lactic acid) grades, a semi-crystalline and an amorphous one, was studied in order to establish a baseline degradation mechanism and kinetics. In particular, the water uptake, the molecular weight, the carboxylic end groups concentration and the thermal properties were monitored during the course of humidity and temperature conditioning at 70 °C and 80% relative humidity (RH), revealing significant extent of chain scission. The effect of four commercial anti-hydrolysis agents of different composition was then examined in order to stabilize the two PLA grades. The additives comprised an epoxy-based chain extender, an aromatic carbodiimide, as well as an aromatic and an aliphatic polycarbodiimide. The epoxy-based additive did not exhibit any stabilizing effect, while the other three carbodiimide-based additives were found efficient as anti-hydrolysis agents at a concentration of 1% especially in the case of the amorphous grade

Artificial weathering and accelerated heat aging studies on low-density polyethylene (Ldpe) produced via autoclave and tubular process technologies

Accelerated (artificial) weathering and thermal aging tests were performed to investigate the effectiveness of different formulations in reducing the UV/heat degradation extent for two low-density polyethylene types (LDPE-A, LDPE-T). The two LDPEs differ in the type and extent of branching due to the applied polymerization process, with LDPE-A being produced in an autoclave and LDPE-T in a tubular reactor. Oligomeric or high molecular weight hindered amine light stabilizer (HALS), and two UV absorbers of benzophenone or hydroxyphenyl-triazine types were equally introduced to both the LDPE grades at a total content of 0.2 wt%. The surface morphology, as well as thermal and mechanical properties, were examined during aging showing a significant degradation extent for the neat samples. In particular, a mechanism of chain scission/branch-ing that resulted in crosslinking was assumed for the neat polyethylenes, after combining the decrease of molecular weight observed in the GPC analysis with the increase in Young's modulus after UV exposure. LDPE-T presented higher photo-ox-idation rates due to its comb-like branched structure and its higher possibility of intermolecular reactions between adjacent chains. Little or no degradation was observed for the stabilized grades, confirming the effectiveness of the selected UV/heat systems in improving the weathering resistance of the two LDPE grades and enhancing their useful lifetime.This publication was made possible by the NPRP award (NPRP 9-161-1-030) from the Qatar National Research Fund (a member of The Qatar Foundation). We are also grateful to BASF and Sabo for supplying the additives at no cost. The statements made herein are solely the responsibility of the author(s).Scopu

Development of value-added polyethylene grades with extended service lifetime: Weathering resistant flame retarded materials for outdoor applications

The current article deals with the development of different novel, tailor-made polyolefin formulations exhibiting both low flammability and high weathering resistance, so as to provide value-added polyethylene grades with extended service lifetime. Two low-density (LDPE) and one linear low-density (LLDPE) polyethylene grades were modified via melt compounding with an additive system comprising: (a) a nitrogen-phosphorous intumescent system for flame retardance and (b) a hindered amine light stabilizer and a benzophenone-type UV absorber for UV/heat stabilization, at a total loading of 30-35 wt%. The target was to reach V0 classification in UL94V flammability tests, while to a large extent maintaining the mechanical properties, such as, tensile and impact strength of the investigated polymers, thus ensuring that the additives do not interfere significantly with the material quality. Subsequently, the compounds were subjected to separate artificial UV and heat aging at 100 C for 1500 h; the formulations showed good flame retardance, even after prolonged artificial weathering, but there was an observable, although acceptable, decrease in the mechanical properties. Nevertheless, all the results show that the developed polyethylene compounds are very promising for outdoor applications, such as, irrigation piping and profiles, where long-term weathering stability is important, and where flame retardance is important for safety during storage.This publication was made possible by the NPRP award (NPRP 9-161-1-030) from the Qatar National Research Fund (a member of The Qatar Foundation). We are also grateful to BASF and Sabo for supplying the additives at no cost. We further express our gratitude to Dr. Mabrouk Ouederni from QAPCO for providing us with the three polyethylene grades. The statements made herein are solely the responsibility of the author(s).Scopu