Crystallization behaviour of poly(lactide) in immiscible blend with poly(ε-caprolactone), comparison with solution and melt-mixed blends

Poly(ε-caprolactone)-poly(carbonate) based copolymers, both block and random, were synthetized and characterized by 1H-NMR spectroscopy. The copolymers have been tested as compatibilizers in 80/20 (w/w%) PLA/PCL blends prepared both by melt and solution mixing. The concentration of PCL-PC based copolymer added to the blends was 2 wt%. Compression moulded sheets and solvent cast films were evaluated by GPC (Gel Permeation Chromatography), TGA (Thermogravimetric Analysis), SEM (Scanning Electron Microscopy), PLOM (Polarized Light Optical Microscopy), DSC (Differential Scanning Calorimetry). The addition of the copolymers does not cause an increased miscibility in PLA-PCL phases since a reduction of PCL particles size is not detected in SEM micrographs. At the same time, upon copolymers addition PLA’s Tg value does not decrease in both melt and solution mixed blends. Copolymers addition causes a reduction of molecular weight in melt mixed blends. In particular, the random copolymer (PCL-ran-PC) causes the highest reduction molecular weight in melt mixed blend, since it is characterized by the lower thermal stability as shown in TGA analysis. As result, PLA phase within melt mixed blends containing PCL-PC based copolymers shows a higher tendency to crystallize during both isothermal and non-isothermal DSC experiments. The increased crystallization of PLA phase is attributed to an increase in spherulitic growth kinetics determined by PLOM analysis. Upon molecular weight reduction in melt mixed blends containing copolymers, PLA chains have a higher mobility resulting in an improved motion towards the growing crystal front

Crystallization kinetics as a sensitive tool to detect degradation in poly(lactide)/poly(ε-caprolactone)/ PCL-co-PC copolymers blends

Poly(lactide)/poly(ε-caprolactone) blends (PLA/PCL) with composition 80/20 (w/w%) are immiscible but biodegradable and therefore often studied in the literature. We have prepared 80/20 PLA/PCL blends with and without poly(ε-caprolactone)-co-poly(carbonate) copolymers (block and random). The blends were prepared both by melt extrusion and by solution blending. The concentration of PCL-co-PC copolymers added to the blends was 2 wt%. Compression molded sheets and solvent cast films were evaluated by GPC (Gel Permeation Chromatography), TGA (Thermogravimetric Analysis), SEM (Scanning Electron Microscopy), PLOM (Polarized Light Optical Microscopy) and DSC (Differential Scanning Calorimetry). Copolymer addition causes a reduction of molecular weight in melt mixed blends. In particular, the random copolymer (PCL-ran-PC) causes the highest molecular weight reduction, since it has lower thermal stability, as shown by TGA. PLOM experiments show that these degraded PLA chains in melt-mixed blends can nucleate and grow faster than similar but undegraded PLA chains in solution-mixed blends. As a result, the PLA phase within melt mixed blends containing PCL-co-PC copolymers shows a higher tendency to crystallize during both isothermal and non-isothermal DSC experiments. Upon molecular weight reduction in melt mixed blends containing copolymers, PLA chains have a higher mobility resulting in faster diffusion towards the growing crystal front. Our results show crystallization kinetic measurements, performed by PLOM or DSC, are useful tools to qualitatively detect molecular weight changes produced by degradation of PLA chains, when the molecular weight reduction is not large enough to decrease Tm values

Preparation and characterization of multifunctional bio-based polymers exhibiting enhanced properties

Driven by environmental reasons and the expected depletion of crude oil, bio-based polymers are currently undergoing a renaissance in the attempt to replace fossil-based ones. The present work aims at contributing in the development of the steps that start from biomass and move to new polymeric multifunctional materials. The study focuses on two bio-based building blocks (itaconic and vanillic acids) characterized by exploitable functionalities, i.e. a lateral double bond and a substituted aromatic ring respectively, able to confer interesting properties to the final polymers. The lateral double bond of dimethyl itaconate was functionalized via thia-Michael addition reaction obtaining a thermo-stable building block that can undergo polycondensation under classical conditions of reaction. The addition of a long lateral chain allows the polymer to express antimicrobial activity against Staphylococcus aureus making it attractive for packaging and targeting antimicrobial applications. Moreover, the architecture of the homopolymer was modified by means of copolymerization with dimethyl 2,5-furandicarboxylate thus improving the rigidity and obtaining a thermo-processable material. Potential applications as thermoset or thermoplastic material have been discussed. As concerns vanillic acid, the presence of aromatic rings on the polymer backbone imparts high thermal stability, but brittle behaviour in the homopolymer. Therefore, the architecture of the polyester was successfully tuned by means of copolymerization with a flexible bio-based comonomer, i.e. ω-pentadecalactone, providing processable random copolymers. An in depth investigation of water transport mechanism has been undertaken on the synthesized polyesters. Since the copolymers present a succession of aromatic and aliphatic units, as a consequence of the chemical structure water vapor permeability interposes between polyethylene and poly(ethylene terephthalate) proving that the copolyesters are suitable for packaging applications. Moving towards a sustainable model of development, novel sustainable synthetic pathways for the eco-design of new bio-based polymeric structures with high value functionalities and different potential applications have been successfully developed

Thia-Michael Reaction for a Thermostable Itaconic-Based Monomer and the Synthesis of Functionalized Biopolyesters

A new building block, derived from dimethyl itaconate, has been synthesized through thia-Michael addition reaction and then exploited for the synthesis of a series of novel aliphatic polyesters. The new monomer, the dimethyl 2-((octylthio)methyl)succinate, demonstrated a remarkable stability toward common conditions of polycondensation (high temperatures and metal-based catalysts) and was suitable for polycondensation reactions with different diols. The resulting polyesters are characterized by high molecular weights and good stability; they are amorphous polymers with a tunable glass transition temperature depending on the rigidity of the diol. The synthetic approach presented here allows, for the first time, remarkably stable polymeric structures based on itaconic acid, circumventing its inherent thermal lability, to be achieved. Furthermore, by demonstration of the successful exploitation of thia-Michael adducts in polymer science, the bases have been set for the creation of a novel renewable platform based on dimethyl itaconate

From Biomass to Bio‐Based Polymers: Exploitation of Vanillic Acid for the Design of New Copolymers with Tunable Properties

Vanillic acid represents a potentially interesting bio-based building block for the production of new aliphatic-aromatic polymers, characterized by thermal properties similar to those of the analogous terephthalic polyesters. However, poly(ethylene vanillate) proved to be a very brittle material, probably due to a very high degree of crystallinity, and, then, not suitable for melt processing. Therefore, the synthesis of copolymers, based on vanillic acid and pentadecalactone is considered as a strategy to obtain new polymeric materials with a low degree of crystallinity, tunable properties and better performances. The synthesis of these fully bio-based random copolymers was successful. The thermal properties have been studied in order to correlate chemical structure and final performances. The polymers proved to be processable and films were obtained, suggesting possible applications of the copolymers in a new sustainable flexible packaging

Water Vapor Sorption and Diffusivity in Bio-Based Poly(ethylene vanillate)—PEV

International audienceThe dynamic and equilibrium water vapor sorption properties of amorphous and highly crystalline poly(ethylene vanillate) (PEV) films were determined via gravimetric analysis, at 20 °C, over a wide range of relative humidity (0–95% RH). At low RH%, the dynamic of the sorption process obeys Fick’s law while at higher relative humidity it is characterized by a drift ascribable to non-Fickian relaxations. The non-Fickian relaxations, which are responsible for the incorporation of additional water, are correlated with the upturn of the sorption isotherms and simultaneously the hysteresis recorded between sorption and desorption cycles. The sorption isotherms of amorphous and highly crystalline PEV are arranged in the same concentration range of that of PET proving the similarity of the two polyesters. Water diffusion coefficients, whose determination from individual kinetic sorption/desorption curves required treatment with the Barens–Hopfenberg model, were demonstrated to be ≈10× higher for amorphous PEV compared to amorphous PET. Such a difference originates from the enhanced segmental flexibility of PEV chains

End of Life of Biodegradable Plastics: Composting versus Re/Upcycling

none8noNowadays the issues related to the end of life of traditional plastics are very urgent due to the important pollution problems that plastics have caused. Biodegradable plastics can help to try to mitigate these problems, but even bioplastics need much attention to carefully evaluate the different options for plastic waste disposal. In this Minireview, three different end-of-life scenarios (composting, recycling, and upcycling) were evaluated in terms of literature review. As a result, the ability of bioplastics to be biodegraded by composting has been related to physical variables and materials characteristics. Hence, it is possible to deduce that the process is mature enough to be a good way to minimize bioplastic waste and valorize it for the production of a fertilizer. Recycling and upcycling options, which could open up many interesting new scenarios for the production of high-value materials, are less studied. Research in this area can be strongly encouraged.mixedClaudio Gioia, Greta Giacobazzi, Micaela Vannini, Grazia Totaro, Laura Sisti, Martino Colonna, Paola Marchese, Annamaria CelliClaudio Gioia, Greta Giacobazzi, Micaela Vannini, Grazia Totaro, Laura Sisti, Martino Colonna, Paola Marchese, Annamaria Cell