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Abstract: A series of N-methyl quaternized derivatives of poly(4-vinylpyridine) (PVP) were synthesized in high yields with different degrees of quaternization, obtained by varying the methyl iodide molar ratio and affording products with unexplored optical and solvation properties. The impact of quaternization on the physicochemical properties of the copolymers, and notably the solvation properties, was further studied. The structure of the synthesized polymers and the quaternization degrees were determined by infrared and nuclear magnetic spectroscopies, while their thermal characteristics were studied by differential scanning calorimetry and their thermal stability and degradation by thermogravimetric analysis (TG-DTA). Attention was given to their optical properties, where UV-Vis and diffuse reflectance spectroscopy (DRS) measurements were carried out. The optical band gap of the polymers was calculated and correlated with the degree of quaternization. The study was further orientated towards the solvation properties of the polymers in binary solvent mixtures that strongly depend on the degree of quaternization, enabling a better understanding of the key polymer (solute)-solvent interactions. The assessment of the underlying solvation phenomena was performed in a system of different ratios of DMSO/H2O and the solvatochromic indicator used was Reichardt’s dye. Solvent polarity parameters have a significant effect on the visible spectra of the nitrogen quaternization of PVP studied in this work and a detailed path towards this assessment is presented.
Keywords: poly(4-vinylpyridine), poly(N-methyl-4-vinylpyridinium iodide), quaternization, solvatochromism, preferential solvation, optical energy gap
Published in DKUM: 26.03.2025; Views: 0; Downloads: 2
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Abstract: Despite the advantages of polylactide (PLA), its inadequate UV-shielding and gas-barrier properties undermine its wide application as a flexible packaging film for perishable items. These issues are addressed in this work by investigating the properties of melt-mixed, fully bioderived blends of polylactide (PLA) and poly(ethylene furanoate) (PEF), as a function of the PEF weight fraction (1–30 wt %) and the amount of the commercial compatibilizer/chain extender Joncryl ADR 4468 (J, 0.25–1 phr). J mitigates the immiscibility of the two polymer phases by decreasing and homogenizing the PEF domain size; for the blend containing 10 wt % of PEF, the PEF domain size drops from 0.67 ± 0.46 µm of the uncompatibilized blend to 0.26 ± 0.14 with 1 phr of J. Moreover, the increase in the complex viscosity of PLA and PLA/PEF blends with the J content evidences the effectiveness of J as a chain extender. This dual positive contribution of J is reflected in the mechanical properties of PLA/PEF blends. Whereas the uncompatibilized blend with 10 wt % of PEF shows lower mechanical performance than neat PLA, all the compatibilized blends show higher tensile strength and strain at break, while retaining their high elastic moduli. The effects of PEF on the UV- and oxygen-barrier properties of PLA are also remarkable. Adding only 1 wt % of PEF makes the blend an excellent barrier for UV rays, with the transmittance at 320 nm dropping from 52.8% of neat PLA to 0.4% of the sample with 1 wt % PEF, while keeping good transparency in the visible region. PEF is also responsible for a sensible decrease in the oxygen transmission rate, which decreases from 189 cc/m2 ·day for neat PLA to 144 cc/m2 ·day with only 1 wt % of PEF. This work emphasizes the synergistic effects of PEF and J in enhancing the thermal, mechanical, UV-shielding, and gas-barrier properties of PLA, which results in bioderived blends that are very promising for packaging applications.
Keywords: polylactide, furanoates, poly(ethylene furanoate), blends, compatibilization, gas-permeability, UV-shielding
Published in DKUM: 24.03.2025; Views: 0; Downloads: 3
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Abstract: This study addresses the inherent shortcomings of poly (lactic acid) (PLA), a biodegradable polymer widely used in industries such as packaging and biomedical applications. The principal challenge of PLA resides in its low crystallinity, which detrimentally affects its mechanical properties and thermal stability. Additionally, PLA is prone to water and hydrolysis, which compromises its chemical resistance and can lead to degradation over time. To overcome surmount these limitations, the study focuses on the development of hybrid films through the blending of PLA with poly (l-lactide-co-ethylene adipate) (pLEA) block copolymers. The objective is to augment the crystallinity, mechanical performance, and chemical resistance of the resulting materials. The study employs a range of analytical techniques, including Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Polarised Light Microscopy (PLM), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA), to thoroughly characterize the copolymers and blend films. By systematically selecting blending ratios and processing methodologies, the study demonstrates enhancements in the properties of the resultant hybrid films compared to neat PLA. Specifically, the structure of films significantly changed from amorphous to crystalline in a short duration - 5 min, of annealing., leading to better tensile strength, modulus and reduced wettability, which are crucial for applications requiring durability and resistance to environmental factors. Films made from 30 wt% of pLEA 97.5/2.5 with 70 % of PLA by fast cooling exhibited outstanding mechanical properties, with a tensile strength 20 MPa higher than that of neat PLA films. Additionally, the chemical resistance may be improved, as evidenced by a decrease in wettability by approximately 15° and a reduction in the polar component of the surface free energy by about 7 mN/m. Hydrophobic, water-repellent materials resist penetration by water and other polar solvents, reducing exposure to corrosive substances and enhancing chemical resistance through barrier protection. Overall, this research addresses the limitations of PLA through innovative copolymerization and blending strategies, offering valuable insights into optimizing the material's properties for various practical applications.
Keywords: Poly(lactic acid), Poly(l-lactide-co-ethylene adipate), copolymer, blend, crystallinity
Published in DKUM: 13.03.2025; Views: 0; Downloads: 7
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Abstract: Poly(ethylene 2,5-furan dicarboxylate) (PEF) based nanocomposites containing different nanoparticles like Ag, TiO2, ZnO, ZrO2 Ce-Bioglass, have been synthesized via in-situ polymerization techniques targeting food pack aging applications. Zeta potential measurements showed an increase in the negative zeta potential value due to an increase in the surface charge density of the nanocomposites. Thermogravimetric analysis results proved that, except PEF-ZnO nanocomposite, all the other nanocomposites exhibited good resistance to thermal degradation without serious mass loss until 330 ◦C. Thermal decomposition kinetic analysis and the dependence of activation energy on the degree of conversion (α), indicated that the presence of ZnO nanoparticles influences, the degradation mechanism of PEF. In contrast, the presence of Ce-Bioglass nanoparticles leads to a slower degra dation process, contributing to the enhanced resistance to thermal degradation of the PEF-Bioglass nano composite. The thermal degradation mechanism of PEF nanocomposites analyzed by pyrolysis‒gas chromatography/mass spectrometry (Py-GC/MS) indicated that the primary thermal degradation mechanism for the studied nanocomposites was β-hydrogen bond scission, while to a lesser extent, α-hydrogen bond scission products were noted in PEF-TiO2 and PEF-ZrO2 nanocomposites.
Keywords: bio based polymers, Poly(ethylene 2, 5-furan dicarboxylate), nanoparticles, thermal properties, nanocomposites, decomposition mechanism
Published in DKUM: 13.03.2025; Views: 0; Downloads: 4
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Abstract: Furanoate polyesters are an extremely promising new class of materials for packaging applications, particularly furanoate-based nanocomposites, which have gained a high interest level in research and development in both academia and industries. The monomers utilised for the synthesis of furanoate-based polyesters were derived from lignocellulosic biomass, which is essential for both eco-friendliness and sustainability. Also, these polyesters have a lower carbon footprint compared to fossil-based plastics, contributing to greenhouse gas reduction. The furanoate-based nanocomposites exhibit enhanced performance characteristics, such as high thermal stability, excellent mechanical strength, superior barrier resistance, and good bacteriostatic rate, making them suitable for a wide range of industrial applications, especially for food-packaging applications. This paper reviews the recent trends in the synthesis routes of monomers, such as the various catalytic activities involved in the oxidation of 5(hydroxymethyl)furfural (HMF) into 2,5-furandicarboxylic acid (FDCA) and its ester, dimethyl furan-2,5-dicarboxylate (DMFD). In addition, this review explores the fabrication of different furanoate-based nanocomposites prepared by in situ polymerization, by melt mixing or solvent evaporation methods, and by using different types of nanoparticles to enhance the overall material properties of the resulting nanocomposites. Emphasis was given to presenting the effect of these nanoparticles on the furanoate polyester’s properties.
Keywords: 2, 5-furandicarboxylic acid, dimethyl furan-2, 5-dicarboxylat, furanoate polyesters, furanoate nanocomposites, thermal properties, mechanical properties, antibacterial properties, sustainable packaging
Published in DKUM: 10.03.2025; Views: 0; Downloads: 5
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