Thermo-oxidative stabilization of poly(lactic acid) with antioxidant intercalated layered double hydroxides
Two antioxidant modified layered double hydroxides (AO-LDHs) were successfully prepared by the intercalation of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (IrganoxCOOH) and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox) in the layered structure of LDH. It was found that by anchoring the phenolic moieties to the LDH layers the antioxidant power is retained in the case of Trolox, and even amplified in the case of IrganoxCOOH. A small amount of the two AO-LDHs was incorporated into poly(lactic acid), PLA, by solution mixing and melt extrusion. The thermo-oxidative stability of the composites was compared with that of the neat PLA and PLA containing free AOs. SEC analy…
Grafting of Hindered Phenol Groups onto Ethylene/α-Olefin Copolymer by Nitroxide Radical Coupling
The covalent immobilization of hindered phenol groups, with potential antioxidant activity, onto an ethylene/α-olefin (EOC) copolymer was carried out by the nitroxide radical coupling (NRC) reaction performed in the melt with a peroxide and the 3,5-di-tert-butyl-4-hydroxybenzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (BHB-T). Functionalized EOC (EOC-g-(BHB-T)) was exposed to photo- and thermo-oxidation. By comparison with some model compounds bearing the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) moiety or the hindered phenol unit, it was observed that the grafted BHB-T could effectively help the stabilization of the polymer matrix both under photo- and thermo-oxidation. In addit…
Recycling ground tire rubber (GTR) scraps as high-impact filler of in situ produced polyketone matrix
A sustainable procedure for recycling powdered rubber coming from scrap tires (ground tire rubber [GTR]) is proposed as based on the dispersion in polyketone (PK) matrix, obtained in situ by CO/ethylene copolymerization. Three types of catalysts are used operative in solvents of different polarities. The catalyst productivity and the hybrids morphology are evaluated and optimized to final composites features. The obtained products are characterized by scanning electron microscopy, atomic force microscopy, and solvent extractions in order to investigate the occurrence and the extent of interactions between PK macromolecular chains and the GTR components; and their effects on the final proper…
Comparison of Different Processing Methods to Prepare Poly(lactid acid)–Hydrotalcite Composites
The effect of the compounding method on the morphology and on the properties of poly(lactic acid) (PLA)-hydrotalcite (HT) composites was studied. Moreover, the influence of two different kinds of HT - organically modified (OM-HT) and unmodified (U-HT) - and their concentration was evaluated. The composites were prepared using either a single screw extruder (SSE), a counter rotating twin-screw compounder (TSC) or a corotating twin-screw extruder (TSE). The prepared materials were characterized by scanning electron microscopy, gel permeation chromatography (GPC) analysis, mechanical and rheological measurements. The results indicated that the best morphology, i.e., particles dimension and dis…
Progress in Understanding of the Interactions between Functionalized Polyolefins and Organo-Layered Double Hydroxides
The dispersion of organo-layered double hydroxides (O-LDH) in functionalized polyolefins (POs) is investigated. Two different polyethylene matrices (maleic anhydride (MAH) and diethyl maleate functionalized) are tested and a hydrogenated fatty acid modified LDH is used. The attention is focused on evidencing the interaction between the functional groups of the polymer and the O-LDH through FT-IR. Moreover, a combination of solvent fractionation, morphological, and rheological characterizations enables to gain a deeper insight into the structure of these composites. In particular, the formation of bridging bonds between the particles and MAH functionalized macromolecules is assumed, possibly…
Time-resolved rheology as a tool to monitor the progress of polymer degradation in the melt state – Part II: Thermal and thermo-oxidative degradation of polyamide 11/organo-clay nanocomposites
Abstract Thermal and thermo-oxidative degradation of nanocomposites based on polyamide 11 (PA11) and organo-modified clay (Cloisite® 30B) are studied in the melt state (T = 215 °C) via time-resolved mechanical spectroscopy (TRMS). The goal is assessing the potentiality of rheological analysis for studying polymer degradation in complex systems such as polymer nanocomposites, whose rheological response stems from the combination of the contributions of polymer and nanoparticles. We prove that a thorough analysis grounded on TRMS allows to isolate the effect of degradation of the polymer matrix, whose progress can be hence profitably monitored. Essentially the same degradation mechanisms as i…
An insight into the interaction between functionalized thermoplastic elastomer and layered double hydroxides through rheological investigations
Abstract Nanocomposites based on maleated poly(styrene-(ethylene-co-butylene)-styrene) copolymer (SEBSgMA) and organo-modified layered double hydroxide (OLDH) have been formulated with the aim to investigate the effects of interfacial interactions between the grafted maleic anhydride groups of the copolymer and the OLDH nanolayers on the rheological properties of nanocomposites. The spectroscopic analysis indicates the establishment of specific polymer/nanofiller interactions, whose extent has been highlighted through morphological and rheological investigations. Specifically, oscillatory melt rheology and shear relaxation tests have been considered in order to deeply investigate the interf…
Grafting of polymer chains on the surface of carbon nanotubes via nitroxide radical coupling reaction
Poly(butylene succinate) (PBS) was grafted on the surface of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) modified multi-walled carbon nanotubes (MWCNTs) via a nitroxide radical coupling reaction. TEMPO functionalized MWCNTs (MWCNTs-g-TEMPO) were synthesized using the Cu(I)-catalyzed azide/alkyne click chemistry approach and the covalent bond of the nitroxide moieties onto the MWCNTs was confirmed via electron paramagnetic resonance (EPR) spectroscopy. The PBS grafting on the sidewalls of MWCNTs was carried out in solution via peroxide-induced formation of macroradicals and it was confirmed by EPR and attenuated total reflectance Fourier transform infrared analysis. Preliminary rheological …
Functionalization of aliphatic polyesters by nitroxide radical coupling
Functionalized poly(butylene succinate) (PBS) samples were prepared by a post-polymerization method based on the coupling reaction between TEMPO derivatives bearing different functionalities and PBS macroradicals generated by H-abstraction using a peroxide. 4-Benzoyloxy-2,2,6,6-tetramethylpiperidine-1- oxyl (BzO-TEMPO) and 4-(1-naphthoate)-2,2,6,6-tetramethylpiperidine-1-oxyl (NfO-TEMPO), a pro-fluorescent nitroxide, were successfully grafted on PBS, as revealed by MALDI TOF MS and UV-Vis spectroscopy. The functionalization degrees were accurately determined by UV-Vis analysis and confirmed by 1H-NMR spectroscopy. The grafting site was identified by combining theoretical calculations with e…