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…
α-Tocopherol-induced radical scavenging activity in carbon nanotubes for thermo-oxidation resistant ultra-high molecular weight polyethylene-based nanocomposites
?-Tocopherol, a natural antioxidant molecule, was physically immobilized on the outer surface of multi-walled carbon nanotubes (CNTs), and the resulting functionalised particles (f-CNTs) were dispersed in ultra-high molecular weight polyethylene aiming at improving its thermo-oxidation resistance. The success of the functionalization was assessed through spectroscopic and thermal analysis, and the influence of the filler on the thermo-oxidative stability of the nanocomposites was investigated through rheological analyses and infrared spectroscopy. We found that the addition of only 1 wt.% of f-CNTs brings about a surprisingly high oxidation resistance, with a five/ten-fold increase of the i…
Multi-functional hindered amine light stabilizers-functionalized carbon nanotubes for advanced ultra-high molecular weight Polyethylene-based nanocomposites
Hindered Amine Light Stabilizer (HAS) molecules have been covalently linked on the outer surface of multi-walled carbon nanotubes (CNTs), and the so-obtained multi-functional fillers (HAS-f-CNTs) have been compounded with Ultra High Molecular Weight Polyethylene (UHMWPE) to get composite films. The success of the grafting reaction of the HAS molecules has been confirmed through spectroscopic and thermo-gravimetric analyses. Morphological analyses reveal a segregated microstructure, in which CNT-rich channels surround the polymer domains. This morphology results in improved mechanical properties and appreciable electrical conductive features. More importantly, the addition of only 1 wt.% of …
Immobilization of natural anti-oxidants on carbon nanotubes and aging behavior of ultra-high molecular weight polyethylene-based nanocomposites
The use of natural antioxidants is an attractive way to formulate nanocomposites with extended durability and with potential applications in bio-medical field. In this work, Vitamin E (VE) in the form of α-tocopherol and Quercetin (Q) are physically immobilized on the outer surface of multi-walled carbon nanotubes (CNTs). Afterward, the CNTs-VE and CNTs-Q are used to formulate thermally stable ultra high molecular weight polyethylene based nanocomposites. The obtained results in the study of the thermo-oxidation behavior suggest a beneficial effect of the natural anti-oxidant carbon nanotubes systems. The unexpected excellent thermo-resistance of the nanocomposites seems to be due to a syne…
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…
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…