Polylactide (PLA) is known as one of the most promising biopolymers as it is derived from renewable feedstock and can be biodegraded. During the last two decades, it moved more and more into the focus of scientific research and industrial use. It is even considered as a suitable replacement for standard petroleum-based polymers, such as polystyrene (PS), which can be found in a wide range of applications—amongst others in foams for packaging and insulation applications—but cause strong environmental issues. PLA has comparable mechanical properties to PS. However, the lack of melt strength is often referred to as a drawback for most foaming processes. One way to overcome this issue is the incorporation of chemical modifiers which can induce chain extension, branching, or cross-linking. As such, a wide variety of substances were studied in the literature. This work should give an overview of the most commonly used chemical modifiers and their effects on rheological, thermal, and foaming behavior. Therefore, this review article summarizes the research conducted on neat and chemically modified PLA foamed with the conventional foaming methods (i.e., batch foaming, foam extrusion, foam injection molding, and bead foaming).
Biodegradable plastics can make an important contribution to the struggle against increasing environmental pollution through plastics. However, biodegradability is a material property that is influenced by many factors. This review provides an overview of the main environmental conditions in which biodegradation takes place and then presents the degradability of numerous polymers. Polylactide (PLA), which is already available on an industrial scale, and the polyhydroxyalkanoates polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-valerate (PHBV), which are among the few plastics that have been proven to degrade in seawater, will be discussed in detail, followed by a summary of the degradability of further petroleum-, cellulose-, starch-, protein- and CO2-based biopolymers and some naturally occurring polymers.
The cyclic amide ε-caprolactam (ε-CLA) is efficiently polymerized by thermally latent C-2-protected N-heterocyclic carbenes (NHCs) to give the corresponding polyamide (PA 6). Carbon dioxideand metal salt-protected NHCs were used as precatalysts, out of which the free carbenes were generated thermally. This way, a premixing of the corresponding initiator with ε-CLA was possible to yield a storable and directly polymerizable mixture. The screening of a variety of differently constituted carbenes showed the importance of basicity of the active species, thereby revealing N-alkyl-bearing tetrahydropyrimidinium-based carbenes as the most active ones. Rapid production of PA 6 in high yields was possible in bulk polymerization at 180 °C, the best activity displayed by 1,3-dicyclohexyltetrahydropyrimidinium-2-carboxylate (6-Cy-CO 2 ). In situ rheology during polymerization showed the characteristics typical for the anionic polymerization of ε-CLA.
Laurolactam (LL) is polymerized in the bulk using strongly basic N-heterocyclic carbenes (NHCs) as initiators at temperatures of 180−200 °C to prepare the corresponding polyamide (PA 12). In-situ rheology of the polymerization progress reveals that an anionic mechanism is active, which is supported by the strong dependence of initiator activity on the basicity of the NHCs. GPC data and kinetic investigations show the process to be moderately controlled and fast, allowing high or quantitative yields in short polymerization times. Fifteen different NHC−CO 2 −adducts and NHC−metal complexes were used as thermally labile but room temperature stable NHC-precursors. Depending on the ring size and N-substituent, some of these protected NHCs allow forming a mixture of monomer and NHC-precursor that is suitable for long-term storage and readily polymerizable by simple heating. All polymerizations are executed without activator or other additives and thus represent a true one-component system for the production of PA 12. Finally, LL is copolymerized with εcaprolactam (ε-CLA). It is found that a copolymer with a considerable gradient is formed, with ε-CLA being incorporated preferentially at the onset of the polymerization.
Incorporation of agricultural wastes as fillers in fiber-reinforced plastics is gaining momentum in plastics engineering research. In this study, fiber-reinforced polypropylene (PP) with rice and coffee husks as filler material were developed. The effect of alkali (sodium hydroxide) pretreatment of the husks on mechanical and thermal properties of developed PP biocomposites was observed. Filler material loading was varied from 0% to 20% for rice husks and 0% to 10% for coffee husks. A twin-screw extruder was used for compounding the PP matrix with rice and coffee husk filler materials. Tensile strengths and percentage elongation results varied from 27.4 to 37.4 MPa and 2.4% to 70.3% (unmodified coffee husks), 31.1 to 37.4 MPa and 5% to 70.3% (unmodified rice husks), 30.7 to 37.4 MPa and 5.3% to 70.3% (modified coffee husks), and 30.7 to 37.4 MPa and 4.8% to 70.3% (modified rice husks). Young’s modulus ranged between 1656 and 2247.8 MPa for biocomposite PP samples with unmodified filler material. Young’s modulus ranged between 1740 and 2160 MPa after alkali treatment of the filler material. Charpy impact strengths ranged from 1.2 to 4 kJ/m2 and 3.1 to 19.6 kJ/m2 for samples containing unmodified and modified filler material, respectively. Thermogravimetric analysis showed that an increase in filler content resulted into delayed weight loss at high degradation temperatures. The results suggest that these developed fiber-reinforced plastics can be used in applications requiring high thermal stability and good mechanical properties.
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