Special Issue "State-of-the-Art Polymer Science and Technology in Italy (2019,2020)"

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (30 June 2020).

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A printed edition of this Special Issue is available here.

Special Issue Editors

Prof. Dr. Ignazio Blanco
Website SciProfiles
Guest Editor
Department of Civil Engineering and Architecture, University of Catania, Edificio 10, Viale A. Doria 6, 95125 Catania, Italy
Interests: thermal stability; thermogravimetric analysis; differential scanning calorimetry; nanocomposites; kinetics of degradation; lifetime prediction; POSS; POSS-Based polymers
Special Issues and Collections in MDPI journals
Prof. Dr. Roberto Pantani
Website
Guest Editor
Industrial Engineering Department, University of Salerno, I-84084 Fisciano (Salerno), Italy
Interests: analysis and simulation of injection moulding of thermoplastics; structure development in polymer processing; volume accuracy and stability in polymer processing; processing and degradation of biodegradable polymers
Special Issues and Collections in MDPI journals
Dr. Andrea Sorrentino
Website SciProfiles
Guest Editor
Institute of Polymers, Composites and Biomaterials (IPCB), National Research Council of Italy (CNR), Via Previati 1/C, 23900 Lecco, Italy
Interests: process–properties relashionships; morphology and properties of polymeric materials; polymer processing; injection and compression moulding; nanofunctionalized polymer materials for barrier and electrical applications; polymer (bio/photo)-degradation; bionanocomposites materials; thermomechanical properties; biodegradable materials; high performances composite materials; materials for sensing; materials for drug delivery; self-healing materials
Special Issues and Collections in MDPI journals
Prof. Dr. Antonio Pizzi
Website
Guest Editor
LERMAB, Laboratoire d’Etude et de Recherche sur le MAteriau Bois, Université de Lorraine, 27 rue Philippe Seguin, CS60036, 88021 Epinal, France
Interests: polycondensation; resins; adhesives; thermosetting polymers for adhesives; natural polymers for industrial use; fibrous and wood composites; polymeric wood constituents (cellulose, lignin, tannins)
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleagues,

Polymer Science and Technology in Italy represents a long-lasting and interdisciplinary field in which chemistry, physics, and engineering mix together to produce studies which are considered among the best in the world. Several research groups coming from very different fields often collaborate in the design of the material, of the part, and of the processing technology to obtain innovative products with outstanding, new, and smart properties. Examples of the contributions of Italian research in the field are spread out in the top Journals and Conferences throughout the world.

This Special Issue aims at collecting an overview of Polymer Science and Technology in Italy. Research topics include but are not limited to:

Polymer composites and nanocomposites;
Biodegradable polymers;
Polymers with special properties and smart polymers;
Advanced characterization of polymers;
New and innovative polymer processes;
Modeling of polymer processing;
Polymeric materials in Additive Manufacturing;
Process–properties relationships;
Polymeric parts for special applications.

The only limitation is that the main part of the study has to have been carried out in Italy or by Italian researchers.

We do hope that this Special Issue can portray the state of the Polymeric Research in Italy and give the rest of the world a bright image of what is carried out in the field in our country.

Dr. Roberto Pantani
Dr. Andrea Sorrentino
Dr. Ignazio Blanco
Dr. Antonio Pizzi
Guest Editors

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Open AccessEditorial
State-of-the-Art Polymer Science and Technology in Italy
Polymers 2020, 12(8), 1721; https://doi.org/10.3390/polym12081721 - 31 Jul 2020
Abstract
The history of polymers in Italy certainly begins with Giulio Natta and the discovery of isotactic polypropylene [...] Full article

Research

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Open AccessArticle
Epoxy Based Blends for Additive Manufacturing by Liquid Crystal Display (LCD) Printing: The Effect of Blending and Dual Curing on Daylight Curable Resins
Polymers 2020, 12(7), 1594; https://doi.org/10.3390/polym12071594 - 18 Jul 2020
Cited by 1
Abstract
Epoxy-based blends printable in a Liquid Crystal Display (LCD) printer were studied. Diglycidyl ether of bisphenol A (DGEBA) mixed with Diethyltoluene diamine (DETDA) was used due to the easy processing in liquid form at room temperature and slower reactivity until heated over 150 [...] Read more.
Epoxy-based blends printable in a Liquid Crystal Display (LCD) printer were studied. Diglycidyl ether of bisphenol A (DGEBA) mixed with Diethyltoluene diamine (DETDA) was used due to the easy processing in liquid form at room temperature and slower reactivity until heated over 150 ° C. The DGEBA/DETDA resin was mixed with a commercial daylight photocurable resin used for LCD screen 3D printing. Calorimetric, dynamic mechanical and rheology testing were carried out on the resulting blends. The daylight resins showed to be thermally curable. Resin’s processability in the LCD printer was evaluated for all the blends by rheology and by 3D printing trials. The best printing conditions were determined by a speed cure test. The use of a thermal post-curing cycle after the standard photocuring in the LCD printer enhanced the glass transition temperature T g of the daylight resin from 45 to 137 ° C when post-curing temperatures up to 180 ° C were used. The T g reached a value of 174 ° C mixing 50 wt% of DGEBA/DETDA resin with the photocurable resin when high temperature cure cycle was used. Full article
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Open AccessArticle
Delayed Addition of Template Molecules Enhances the Binding Properties of Diclofenac-Imprinted Polymers
Polymers 2020, 12(5), 1178; https://doi.org/10.3390/polym12051178 - 21 May 2020
Cited by 1
Abstract
It has been reported that in the molecular imprinting technique, the use of preformed oligomers instead of functional monomers increases the stability of the non-covalent interactions with the template molecule, providing a sharp gain in terms of binding properties for the resulting imprinted [...] Read more.
It has been reported that in the molecular imprinting technique, the use of preformed oligomers instead of functional monomers increases the stability of the non-covalent interactions with the template molecule, providing a sharp gain in terms of binding properties for the resulting imprinted polymer. Based on this theory, we assumed that the delayed addition of template molecules to a polymerization mixture enhances the binding properties of the resulting polymer. To verify this hypothesis, we imprinted several mixtures of 4-vinylpyridine/ethylene dimethacrylate (1:6 mol/mol) in acetonitrile by adding diclofenac progressively later from the beginning of the polymerization process. After polymerization, the binding isotherms of imprinted and non-imprinted materials were measured in acetonitrile by partition equilibrium experiments. Binding data confirm our hypothesis, as imprinted polymers prepared by delayed addition, with delay times of 5 and 10 min, showed higher binding affinity (Keq = 1.37 × 104 L mol−1 and 1.80 × 104 L mol−1) than the polymer obtained in the presence of template at the beginning (Keq = 5.30 × 103 L mol−1). Similarly, an increase in the imprinting factor measured vs. the non-imprinted polymer in the binding selectivity with respect to mefenamic acid was observed. We believe that the delayed addition approach could be useful in prepar imprinted polymers with higher binding affinity and increased binding selectivity in cases of difficult imprinting polymerization. Full article
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Open AccessArticle
Wear Resistant Nanocomposites Based on Biomedical Grade UHMWPE Paraffin Oil and Carbon Nano-Filler: Preliminary Biocompatibility and Antibacterial Activity Investigation
Polymers 2020, 12(4), 978; https://doi.org/10.3390/polym12040978 - 22 Apr 2020
Cited by 3
Abstract
In the present paper, we investigate the effectiveness of nanocomposites (composed of ultra-high molecular weight polyethylene (UHMWPE) mixed with carbon nano-filler (CNF) and medical grade paraffin oil (PO), from the biological point of view. Wear measurements were carried out without (air) and with [...] Read more.
In the present paper, we investigate the effectiveness of nanocomposites (composed of ultra-high molecular weight polyethylene (UHMWPE) mixed with carbon nano-filler (CNF) and medical grade paraffin oil (PO), from the biological point of view. Wear measurements were carried out without (air) and with lubricant (distilled water, natural, and artificial lubricant), and antibacterial activity and cytotoxicity were evaluated. The results highlighted that the presence of CNF is important in the nanocomposite formulation because it reduces the wear rate and prevents oxidative degradation during its processing. An amount of 1.0 wt % of CNF is best because it reaches the optimal distribution within the polymeric matrix, resulting in the best wear resistant, bio-active, and anti-bacterial nanocomposite among all investigated samples. Full article
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Open AccessArticle
Electrically-Conductive Polyketone Nanocomposites Based on Reduced Graphene Oxide
Polymers 2020, 12(4), 923; https://doi.org/10.3390/polym12040923 - 16 Apr 2020
Cited by 3
Abstract
In this work, we investigated the functionalization of polyketone 30 (PK30) with glycyl-glycine (Gly-Gly) via the Paal–Knorr reaction with the aim of homogenously dispersing two types of reduced graphene oxide (rGO, i.e., lrGO and hrGO, the former characterized by a lower degree of [...] Read more.
In this work, we investigated the functionalization of polyketone 30 (PK30) with glycyl-glycine (Gly-Gly) via the Paal–Knorr reaction with the aim of homogenously dispersing two types of reduced graphene oxide (rGO, i.e., lrGO and hrGO, the former characterized by a lower degree of reduction in comparison to the latter) by non-covalent interactions. The functional PK30-Gly-Gly polymer was effective in preparing composites with homogeneously distributed rGO characterized by an effective percolation threshold at 5 wt. %. All the composites showed a typical semiconductive behavior and stable electrical response after several heating/cooling cycles from 30 to 115 °C. Composites made by hrGO displayed the same resistive behaviour even if flanked by a considerable improvement on conductivity, in agreement with the more reduced rGO content. Interestingly, no permanent percolative network was shown by the composite with 4 wt. % of lrGO at temperatures higher than 45 °C. This material can be used as an ON–OFF temperature sensor and could find interesting applications as sensing material in soft robotics applications. Full article
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Open AccessArticle
Preparation and Characterization of UV-LED Curable Acrylic Films Containing Biochar and/or Multiwalled Carbon Nanotubes: Effect of the Filler Loading on the Rheological, Thermal and Optical Properties
Polymers 2020, 12(4), 796; https://doi.org/10.3390/polym12040796 - 02 Apr 2020
Cited by 2
Abstract
UV-LED curable coatings represent an up-to-date attractive field due to the high curing efficiency even in the presence of high filler loadings, as well as to the absence of infrared wavelengths that may negatively impact on heat-sensitive substrates. The addition of carbonaceous materials, [...] Read more.
UV-LED curable coatings represent an up-to-date attractive field due to the high curing efficiency even in the presence of high filler loadings, as well as to the absence of infrared wavelengths that may negatively impact on heat-sensitive substrates. The addition of carbonaceous materials, such as biochar (BC) and/or multiwalled carbon nanotubes (MWCNTs) could positively improve both the rheological and thermal properties. In this study we report on the synthesis and characterization of carbon-reinforced films containing nanometric (MWCNTs) and micrometric (BC) carbon-based materials. We analyze the rheological properties of the UV-LED curable dispersions, as well as the thermal and optical properties of the resulting films, establishing some correlations between filler dispersion/loading with the main observed properties. Full article
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Open AccessArticle
Coincident Correlation between Vibrational Dynamics and Primary Relaxation of Polymers with Strong or Weak Johari-Goldstein Relaxation
Polymers 2020, 12(4), 761; https://doi.org/10.3390/polym12040761 - 31 Mar 2020
Cited by 1
Abstract
The correlation between the vibrational dynamics, as sensed by the Debye-Waller factor, and the primary relaxation in the presence of secondary Johari-Goldstein (JG) relaxation, has been investigated through molecular dynamics simulations. Two melts of polymer chains with different bond length, resulting in rather [...] Read more.
The correlation between the vibrational dynamics, as sensed by the Debye-Waller factor, and the primary relaxation in the presence of secondary Johari-Goldstein (JG) relaxation, has been investigated through molecular dynamics simulations. Two melts of polymer chains with different bond length, resulting in rather different strength of the JG relaxation are studied. We focus on the bond-orientation correlation function, exhibiting higher JG sensitivity with respect to alternatives provided by torsional autocorrelation function and intermediate scattering function. We find that, even if changing the bond length alters both the strength and the relaxation time of the JG relaxation, it leaves unaffected the correlation between the vibrational dynamics and the primary relaxation. The finding is in harmony with previous studies reporting that numerical models not showing secondary relaxations exhibit striking agreement with experimental data of polymers also where the presence of JG relaxation is known. Full article
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Open AccessArticle
Comparative Investigation on the Soil Burial Degradation Behaviour of Polymer Films for Agriculture before and after Photo-Oxidation
Polymers 2020, 12(4), 753; https://doi.org/10.3390/polym12040753 - 30 Mar 2020
Cited by 5
Abstract
Polymer films based on biodegradable polymers, polyethylene (PE) and modified PE with oxo-degradable additive were prepared by film blowing. Carbon black (1%) was added to all the films. Commercial biodegradable Ecovio® and Mater-Bi® samples were used. Mechanical properties, soil burial degradation [...] Read more.
Polymer films based on biodegradable polymers, polyethylene (PE) and modified PE with oxo-degradable additive were prepared by film blowing. Carbon black (1%) was added to all the films. Commercial biodegradable Ecovio® and Mater-Bi® samples were used. Mechanical properties, soil burial degradation and surface wettability were investigated, before and after UV irradiation. Chemical modifications induced by UV and soil degradation, or a synergic effect, were highlighted by Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR). Photo-oxidized film samples with an elongation at break equal to 50% and 0.5 the initial value were selected for the soil burial degradation test at 30 °C. Weight loss measurements were used to follow biodegradation in soil. Predictably, the degradation in soil was higher for biodegradable polymer-based films than for the PE-based ones. UV irradiation increased surface wettability and encouraged the disintegration in soil of all the samples. In fact, photo-oxidation produced a molar mass reduction and hydrophilic end groups, thus increasing surface erosion and weight loss. This paper not only supplies new criteria to evaluate the performance of biodegradable films in agriculture, before and after lifetime, but also provides a comparative analysis on the soil burial degradation behaviour with traditional ones. Full article
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Open AccessArticle
Synthesis and Characterization of High-Performing Sulfur-Free Tannin Foams
Polymers 2020, 12(3), 564; https://doi.org/10.3390/polym12030564 - 04 Mar 2020
Cited by 2
Abstract
Tannin foams are green lightweight materials that have attracted industrial interest for the manufacturing of sandwich panels for insulation purposes. However, the dimensions of the cells and the presence of sulfur in the formulation developed until now have discouraged their upscaling. In this [...] Read more.
Tannin foams are green lightweight materials that have attracted industrial interest for the manufacturing of sandwich panels for insulation purposes. However, the dimensions of the cells and the presence of sulfur in the formulation developed until now have discouraged their upscaling. In this work, we present the synthesis and the characterization of the more promising small cell and sulfur-free materials. It was observed that, with respect to standard ones, foams catalyzed with nitric acid present similar physical properties and more phenolic character, which favors the absorption of ionic pollutants. Conversely, the foams blown with aliphatic solvents and surfactants present smaller pores, and higher mechanical and insulating properties, without affecting the chemical properties or the heating value. The combined foam produced with nitric acid as a catalyst and petroleum ether as a blowing agent result in sulfur-free and small cell material with overall improved features. These foams have been produced at 30 × 30 × 3 cm3, with high homogeneity and, to date, they represent the most suitable formulation for industrial upscaling. Full article
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Open AccessArticle
Ionic Liquid as Dispersing Agent of LDH-Carbon Nanotubes into a Biodegradable Vinyl Alcohol Polymer
Polymers 2020, 12(2), 495; https://doi.org/10.3390/polym12020495 - 24 Feb 2020
Cited by 5
Abstract
A Zn/Al layered double hydroxides (LDHs) hosting carbon nanotubes (80% of CNTs) was synthesized and dispersed into a commercial biodegradable highly amorphous vinyl alcohol polymer at different loading (i.e., 1; 3; 5; 10 wt %). In order to improve the degree of dispersion [...] Read more.
A Zn/Al layered double hydroxides (LDHs) hosting carbon nanotubes (80% of CNTs) was synthesized and dispersed into a commercial biodegradable highly amorphous vinyl alcohol polymer at different loading (i.e., 1; 3; 5; 10 wt %). In order to improve the degree of dispersion of the filler into the polymer matrix, an ionic liquid (IL) based on 1-hexadecyl-3-methylimidazolium dimethyl-5-sodiosulfoisophthalate was added to the composites’ mixtures. Structural characterization of filler and polymeric composites was carried out. The analysis of thermal, mechanical and electrical properties of the composites, resulted improved compared to the unfilled material, allowed to hypothesize a good dispersion of the LDH-CNTs lamellar filler into the polymer matrix-assisted by the ionic liquid. This was demonstrated comparing electrical conductivity of composite at 5% of LDH-CNTs in the presence and in the absence of IL. The experimental results showed that the electrical conductivity of the sample with IL is four orders of magnitude higher than the one without IL. Furthermore, the percolation threshold of the whole system resulted very low—0.26% of LDH-CNTs loading, which is 0.21% of CNTs. Full article
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Open AccessArticle
Experimental Cold-Cured Nanostructured Epoxy-Based Hybrid Formulations: Properties and Durability Performance
Polymers 2020, 12(2), 476; https://doi.org/10.3390/polym12020476 - 19 Feb 2020
Cited by 2
Abstract
Different hybrid epoxy formulations were produced and cold-cured, monitoring the properties development during low temperature curing and aging. All systems were based on silane functionalized bis-phenol A (DGEBA) resins (Part A), cured at ambient temperature with two amine hardeners (Part B). The different [...] Read more.
Different hybrid epoxy formulations were produced and cold-cured, monitoring the properties development during low temperature curing and aging. All systems were based on silane functionalized bis-phenol A (DGEBA) resins (Part A), cured at ambient temperature with two amine hardeners (Part B). The different components of the formulations were selected on their potential capability to bring about enhancements in the glass transition temperature. The durability of the produced hybrids was probed in comparison to the corresponding neat epoxies by monitoring changes in glass transition temperature (Tg) and flexural mechanical properties after exposure to different levels of humidity and immersion in water and at temperatures slightly higher than the local ambient temperature, in order to simulate the conditions encountered during summer seasons in very humid environments. The thermal degradation resistance of the hybrid systems was also evaluated by thermogravimetric analysis. Full article
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Open AccessArticle
Improvement of Peptide Affinity and Stability by Complexing to Cyclodextrin-Grafted Ammonium Chitosan
Polymers 2020, 12(2), 474; https://doi.org/10.3390/polym12020474 - 19 Feb 2020
Cited by 3
Abstract
Cyclodextrin-grafted polymers are attractive biomaterials that could bring together the host–guest complexing capability of pristine cyclodextrin and the pharmaceutical features of the polymeric backbone. The present paper is aimed at characterizing the potential application of ammonium–chitosan grafted with 2-methyl-β-cyclodextrin (N+-rCh-MCD) as [...] Read more.
Cyclodextrin-grafted polymers are attractive biomaterials that could bring together the host–guest complexing capability of pristine cyclodextrin and the pharmaceutical features of the polymeric backbone. The present paper is aimed at characterizing the potential application of ammonium–chitosan grafted with 2-methyl-β-cyclodextrin (N+-rCh-MCD) as the functional macromolecular complexing agent for the oral administration of the neuropeptide dalargin (DAL). Specific NMR characterization procedures, along with UV and fluorescence techniques, as well as biological in vitro assessments have been performed. The results indicate that N+-rCh-MCD forms water-soluble complexes with DAL, with a prevalent involvement of Tyr or Phe over Leu and Ala residues. The association constant of DAL with the polymeric derivative is one order of magnitude higher than that with the pristine cyclodextrin (Ka: 2600 M−1 and 120 M−1, respectively). Additionally, N+-rCh-MCD shields DAL from enzymatic degradation in gastrointestinal in vitro models with a three-fold time delay, suggesting a future pharmaceutical exploitation of the polymeric derivative. Therefore, the greater affinity of N+-rCh-MCD for DAL and its protective effect against enzymatic hydrolysis can be attributed to the synergistic cooperation between cyclodextrin and the polymer, which is realized only when the former is covalently linked to the latter. Full article
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Open AccessArticle
Effect of Rapid Mold Heating on the Structure and Performance of Injection-Molded Polypropylene
Polymers 2020, 12(2), 341; https://doi.org/10.3390/polym12020341 - 05 Feb 2020
Cited by 1
Abstract
The tailoring by the process of the properties developed in the plastic objects is the more effective way to improve the sustainability of the plastic objects. The possibility to tailor to the final use the properties developed within the molded object requires further [...] Read more.
The tailoring by the process of the properties developed in the plastic objects is the more effective way to improve the sustainability of the plastic objects. The possibility to tailor to the final use the properties developed within the molded object requires further understanding of the relationship between the properties of the plastic objects and the process conduction. One of the main process parameters that allow adjusting the properties of molded objects is the mold temperature. In this work, a thin electrical heater was located below the cavity surface in order to obtain rapid and localized surface heating/cooling cycles during the injection molding process. An isotactic polypropylene was adopted for the molding tests, during which surface temperature was modulated in terms of values and heating times. The modulation of the cavity temperature was found able to control the distribution of relevant morphological characteristics, thus, properties along the sample thickness. In particular, lamellar thickness, crystallinity distribution, and orientation were analyzed by synchrotron X-ray experiments, and the morphology and elastic modulus were characterized by atomic force microscopy acquisitions carried out with a tool for the simultaneous nanomechanical characterization. The crystalline degree slightly increased with the cavity temperature, and this induced an increase in the elastic modulus when high temperatures were adopted for the cavity surface. The cavity temperature strongly influenced the orientation distribution that, on its turn, determined the highest values of the elastic modulus found in the shear layer. Furthermore, although the sample core, not experiencing a strong flow field, was not characterized by high levels of orientation, it might show high values of the elastic modulus if temperature and time during crystallization were sufficient. In particular, if the macromolecules spent adequate time at temperatures close to the crystallization temperature, they could achieve high levels of structuring and, thus, high values of elastic modulus. Full article
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Open AccessArticle
Multifunctional Bioactive Resin for Dental Restorative Materials
Polymers 2020, 12(2), 332; https://doi.org/10.3390/polym12020332 - 05 Feb 2020
Cited by 2
Abstract
Resin-based composites are widely used as dental restorative materials due to their excellent properties. They must have high modulus, high hardness, and be chemically inert while minimizing moisture uptake. To fulfill these higher standard prerequisites and properties, continuous improvements in each of their [...] Read more.
Resin-based composites are widely used as dental restorative materials due to their excellent properties. They must have high modulus, high hardness, and be chemically inert while minimizing moisture uptake. To fulfill these higher standard prerequisites and properties, continuous improvements in each of their components are required. This study develops novel composites with multiple biofunctions. Light-cured Bis-GMA/TEGDMA dental resin (RK)/layered double hydroxide intercalated with fluoride ions (LDH-F)/calcium bentonite (Bt) hybrid composites were prepared. The loading ratio of LDH-F to Bt was varied, ranging from 2.5/2.5 to 10/10 parts per hundred RK and structural, mechanical, and biological properties were studied. The incorporation of even small mass fractions (e.g., 2.5 wt% of LDH-F and 2.5 wt% of Bt) in RK dental resin significantly improved the mechanical properties of the pristine resin. The synthetized materials showed antibacterial and antibiofilm effects against three bacterial strains isolated from healthy volunteers’ saliva (Streptococcus spp., Bacteroides fragilis, and Staphylococcus epidermidis) without affecting its ability to induce dental pulp stem cells differentiation into odontoblast-like cells. The capability to balance between the antibiofilm activity and dental pulp stem cells differentiation in addition with improved mechanical properties make these materials a promising strategy in preventive and restorative dentistry. Full article
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Open AccessArticle
Eudragit: A Novel Carrier for Controlled Drug Delivery in Supercritical Antisolvent Coprecipitation
Polymers 2020, 12(1), 234; https://doi.org/10.3390/polym12010234 - 18 Jan 2020
Cited by 6
Abstract
In this work, the supercritical antisolvent (SAS) process was used to coprecipitate Eudragit L100-55 (EUD) with diclofenac (DICLO) and theophylline (THEOP), with the aim of obtaining composite microparticles with a prolonged drug release for oral delivery. Working at the optimized conditions in terms [...] Read more.
In this work, the supercritical antisolvent (SAS) process was used to coprecipitate Eudragit L100-55 (EUD) with diclofenac (DICLO) and theophylline (THEOP), with the aim of obtaining composite microparticles with a prolonged drug release for oral delivery. Working at the optimized conditions in terms of pressure and overall concentration in the liquid solution (10.0 MPa and 50 mg/mL), microparticles of EUD/DICLO 20/1 and 10/1 w/w were produced with a mean size of 2.92 µm and 1.53 µm, respectively. For the system EUD/THEOP, well-defined spherical microspheres with a mean diameter ranging from 3.75 µm and 5.93 µm were produced at 12.0 MPa. The produced composite systems were characterized by various techniques, such as scanning electron microscopy, differential scanning calorimetry, X-ray microanalysis, FT-IR and UV–vis spectroscopy. Dissolution studies showed the potential of EUD to prolong the drug release, significantly, up to a few days. Full article
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Open AccessArticle
Understanding the Polymerization of Polyfurfuryl Alcohol: Ring Opening and Diels-Alder Reactions
Polymers 2019, 11(12), 2126; https://doi.org/10.3390/polym11122126 - 17 Dec 2019
Cited by 4
Abstract
Polyfurfuryl alcohol (PFA) is one of the most intriguing polymers because, despite its easy polymerization in acid environment, its molecular structure is definitely not obvious. Many studies have been performed in recent decades, and every time, surprising aspects came out. With the present [...] Read more.
Polyfurfuryl alcohol (PFA) is one of the most intriguing polymers because, despite its easy polymerization in acid environment, its molecular structure is definitely not obvious. Many studies have been performed in recent decades, and every time, surprising aspects came out. With the present study, we aim to take advantage of all of the findings of previous investigations and exploit them for the interpretation of the completely cured PFA spectra registered with three of the most powerful techniques for the characterization of solid, insoluble polymers: Solid-State 13C-NMR, Attenuated Total Reflectance (ATR), Fourier Transform Infrared (FTIR) spectroscopy, and UV-resonant Raman spectroscopy at different excitation wavelengths, using both an UV laser source and UV synchrotron radiation. In addition, the foreseen structures were modeled and the corresponding 13C-NMR and FTIR spectra were simulated with first-principles and semi-empiric methods to evaluate their matching with experimental ones. Thanks to this multi-technique approach, based on complementary analytical tools and computational support, it was possible to conclude that, in addition to the major linear unconjugated polymerization, the PFA structure consists of Diels-Alder rearrangements occurring after the opening of some furanic units, while the terminal moieties of the chain involves γ-lactone arrangements. The occurrence of head-head methylene ether bridges and free hydroxyl groups (from unreacted furfuryl alcohol, FA, or terminal chains) could be excluded, while the conjugated systems could be considered rather limited. Full article
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Open AccessArticle
Study on the Printability through Digital Light Processing Technique of Ionic Liquids for CO2 Capture
Polymers 2019, 11(12), 1932; https://doi.org/10.3390/polym11121932 - 23 Nov 2019
Cited by 1
Abstract
Here we present new 3D printable materials based on the introduction of different commercially available ionic liquids (ILs) in the starting formulations. We evaluate the influence of these additives on the printability of such formulations through light-induced 3D printing (digital light processing—DLP), investigating [...] Read more.
Here we present new 3D printable materials based on the introduction of different commercially available ionic liquids (ILs) in the starting formulations. We evaluate the influence of these additives on the printability of such formulations through light-induced 3D printing (digital light processing—DLP), investigating as well the effect of ionic liquids with polymerizable groups. The physical chemical properties of such materials are compared, focusing on the permeability towards CO2 of the different ILs present in the formulations. At last, we show the possibility of 3D printing high complexity structures, which could be the base of new high complexity filters for a more efficient CO2 capture. Full article
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Open AccessArticle
Safely Dissolvable and Healable Active Packaging Films Based on Alginate and Pectin
Polymers 2019, 11(10), 1594; https://doi.org/10.3390/polym11101594 - 29 Sep 2019
Cited by 5
Abstract
Extensive usage of long-lasting petroleum based plastics for short-lived application such as packaging has raised concerns regarding their role in environmental pollution. In this research, we have developed active, healable, and safely dissolvable alginate-pectin based biocomposites that have potential applications in food packaging. [...] Read more.
Extensive usage of long-lasting petroleum based plastics for short-lived application such as packaging has raised concerns regarding their role in environmental pollution. In this research, we have developed active, healable, and safely dissolvable alginate-pectin based biocomposites that have potential applications in food packaging. The morphological study revealed the rough surface of these biocomposite films. Tensile properties indicated that the fabricated samples have mechanical properties in the range of commercially available packaging films while possessing excellent healing efficiency. Biocomposite films exhibited higher hydrophobicity properties compared to neat alginate films. Thermal analysis indicated that crosslinked biocomposite samples possess higher thermal stability in temperatures below 120 °C, while antibacterial analysis against E. coli and S. aureus revealed the antibacterial properties of the prepared samples against different bacteria. The fabricated biodegradable multi-functional biocomposite films possess various imperative properties, making them ideal for utilization as packaging material. Full article
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Open AccessArticle
Photo-Oxidative and Soil Burial Degradation of Irrigation Tubes Based on Biodegradable Polymer Blends
Polymers 2019, 11(9), 1489; https://doi.org/10.3390/polym11091489 - 12 Sep 2019
Cited by 8
Abstract
Irrigation tubes based on biodegradable polymers were prepared via an extrusion-drawing process by Irritec and compared to conventional pipes made of high-density polyethylene (HDPE). A commercial polylactide/poly (butyleneadipate-co-butyleneterephthalate) (PLA/PBAT) blend (Bio-Flex®) and Mater-Bi® were used. The polymers were [...] Read more.
Irrigation tubes based on biodegradable polymers were prepared via an extrusion-drawing process by Irritec and compared to conventional pipes made of high-density polyethylene (HDPE). A commercial polylactide/poly (butyleneadipate-co-butyleneterephthalate) (PLA/PBAT) blend (Bio-Flex®) and Mater-Bi® were used. The polymers were characterized from rheological and mechanical points of view. Irrigation pipes were subjected to photoaging with continued exposure to UV radiation up to 22 days. The degradability in the soil of irrigation tube samples was studied. The influence of temperature and UV irradiation on soil burial degradation was investigated. A soil burial degradation test was carried out at 30 °C and 50 °C for up to 70 days. The degree of degradation was evaluated from the weight loss percentage. The degradation rate of irrigation tube samples based on Mater-Bi® was higher at 30 °C and was stimulated after 14 days of UV irradiation. Higher temperatures or UV aging encouraged the disintegration in soil of Bio-Flex®-based irrigation tubes. Furthermore, tube samples, before and after UV and soil burial degradation, were analyzed by Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR) spectroscopy. Full article
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Open AccessArticle
Reactions of Soy Flour and Soy Protein by Non-Volatile Aldehydes Generation by Specific Oxidation
Polymers 2019, 11(9), 1478; https://doi.org/10.3390/polym11091478 - 10 Sep 2019
Cited by 5
Abstract
Soy protein isolate (SPI) and insoluble soy flour polymeric carbohydrates have been reacted with sodium periodate for the specific oxidation of vicinal –OH groups to investigate the reactions involved in this approach to soy flour adhesives. The reactions have been shown to generate [...] Read more.
Soy protein isolate (SPI) and insoluble soy flour polymeric carbohydrates have been reacted with sodium periodate for the specific oxidation of vicinal –OH groups to investigate the reactions involved in this approach to soy flour adhesives. The reactions have been shown to generate carbohydrate oligomer fractions presenting one, two or multiple aldehyde groups. With the exception of the small molecular weight heptanedial, the smaller molecular weight aldehydes generated from mono- and disaccharides by the same reaction do not appear to form from the insoluble soy flour carbohydrates, or have already reacted. The reaction of periodate with soy protein isolate has been shown to generate some aldehydes too. When the mix of SPI and soy insoluble carbohydrates is treated with periodate, the majority of the observed aldehyde carrying species appear to be higher molecular weight carbohydrate oligomer fractions. Full article
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Open AccessArticle
Polystyrene Nanocomposites Reinforced with Novel Dumbbell-Shaped Phenyl-POSSs: Synthesis and Thermal Characterization
Polymers 2019, 11(9), 1475; https://doi.org/10.3390/polym11091475 - 09 Sep 2019
Cited by 5
Abstract
Two series of novel dumbbell-shaped polyhedral oligomeric silsesquioxanes (POSSs), fully functionalized with phenyl groups at the corner of the silicon cages, were used to prepare polystyrene (PS) nanocomposites through the method of in situ polymerization. The percentage of the molecular filler reinforcement was [...] Read more.
Two series of novel dumbbell-shaped polyhedral oligomeric silsesquioxanes (POSSs), fully functionalized with phenyl groups at the corner of the silicon cages, were used to prepare polystyrene (PS) nanocomposites through the method of in situ polymerization. The percentage of the molecular filler reinforcement was set as 5% w/w of POSS and was checked by 1H-NMR spectroscopy. The obtained nanocomposites were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Thermal and morphological properties were evaluated and compared among the nanocomposites obtained using the two different series of dumbbell-shaped POSSs and with the net PS. The thermal parameters for the prepared nanocomposites were very high when compared with those of neat PS, and they evidenced significant differences when an aliphatic or aromatic bridge was used to link the silicon cages. SEM analysis results allow us to hypothesize a justification for the different resistance to thermal degradation showed by the two series of molecular reinforcement. Full article
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Review

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Open AccessFeature PaperReview
Life-Cycle Assessment in the Polymeric Sector: A Comprehensive Review of Application Experiences on the Italian Scale
Polymers 2020, 12(6), 1212; https://doi.org/10.3390/polym12061212 - 26 May 2020
Cited by 4
Abstract
In recent years, a growing media campaign has demonized the use of plastic tout court, as solely responsible for environmental problems. Behind what is now vulgarly called plastic there are actually many applications and uses without which our daily life would be greatly [...] Read more.
In recent years, a growing media campaign has demonized the use of plastic tout court, as solely responsible for environmental problems. Behind what is now vulgarly called plastic there are actually many applications and uses without which our daily life would be greatly penalized in the most common and routine actions. Our belief, in the role of researchers who have made polymers and their derivatives their main research object, is that sustainable use of polymeric materials is not only possible but is above all necessary. For this reason, in this review which is part of the Special Issue “State-of-the-Art Polymer Science and Technology in Italy”, we offer a rundown of life-cycle assessment (LCA) studies on polymers used in the most important production and commercial sectors carried out in the last few years by Italians researchers. Full article
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Open AccessReview
History of Cyclodextrin Nanosponges
Polymers 2020, 12(5), 1122; https://doi.org/10.3390/polym12051122 - 14 May 2020
Cited by 4
Abstract
Nowadays, research in the field of nanotechnology and nanomedicine has become increasingly predominant, focusing on the manipulation and development of materials on a nanometer scale. Polysaccharides have often been used as they are safe, non-toxic, hydrophilic, biodegradable and are low cost. Among them, [...] Read more.
Nowadays, research in the field of nanotechnology and nanomedicine has become increasingly predominant, focusing on the manipulation and development of materials on a nanometer scale. Polysaccharides have often been used as they are safe, non-toxic, hydrophilic, biodegradable and are low cost. Among them, starch derivatives and, in particular, cyclodextrin-based nanosponges (CD NSs) have recently emerged due to the outstanding properties attributable to their peculiar structure. In fact, alongside the common polysaccharide features, such as the presence of tunable functional groups and their ability to interact with biological tissues, thus giving rise to bioadhesion, which is particularly useful in drug delivery, what makes CD NSs unique is their three-dimensional network made up of crosslinked cyclodextrin units. The name “nanosponge” appeared for the first time in the 1990s due to their nanoporous, sponge-like structure and responded to the need to overcome the limitations of native cyclodextrins (CDs), particularly their water solubility and inability to encapsulate charged and large molecules efficiently. Since CD NSs were introduced, efforts have been made over the years to understand their mechanism of action and their capability to host molecules with low or high molecular weight, charged, hydrophobic or hydrophilic by changing the type of cyclodextrin, crosslinker and degree of crosslinking used. They enabled great advances to be made in various fields such as agroscience, pharmaceutical, biomedical and biotechnological sectors, and NS research is far from reaching its conclusion. This review gives an overview of CD NS research, focusing on the origin and key points of the historical development in the last 50 years, progressing from relatively simple crosslinked networks in the 1960s to today’s multifunctional polymers. The approach adopted in writing the present study consisted in exploring the historical evolution of NSs in order to understand their role today, and imagine their future. Full article
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