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ACS Macro Letters Jun 2024Silyl ether constitutes a multipurpose (macro)molecular functionality for being, e.g., SuFEx-clickable and easily cleavable as a hydroxyl precursor. Its direct...
Silyl ether constitutes a multipurpose (macro)molecular functionality for being, e.g., SuFEx-clickable and easily cleavable as a hydroxyl precursor. Its direct incorporation by anionic polymerization is challenged by its base susceptibility. In this study, a two-component organocatalyst shows strict epoxy-selectivity in the anionic ring-opening polymerization (ROP) of commercially available -butyldimethylsilyl ()-(-)-glycidyl ether (TBSGE). The silyl ether pendant groups are fully preserved in the resultant polyether and readily undergo acidic hydrolysis to yield well-defined linear polyglycerol (PGC). Combination of the ROP with mechanistically distinct polymerization chemistries delivers PGC-based polyurethane and a hybrid amphiphilic block copolymer. The SuFEx reaction with sulfonyl fluoride shows effective tuning of polyTBSGE into a sulfonate-functionalized polyether. We have thus exploited the chemoselectivity of organocatalysis to facilitate access to polymers carrying reactive pendant functionalities.
PubMed: 38934638
DOI: 10.1021/acsmacrolett.4c00356 -
Polymers Jun 2024Despite the mechanical and physical properties of polyurethane foams (PUF), their application is still hindered by high inflammability. The elaboration of effective,...
Despite the mechanical and physical properties of polyurethane foams (PUF), their application is still hindered by high inflammability. The elaboration of effective, low-cost, and environmentally friendly fire retardants remains a pressing issue that must be addressed. This work aims to show the feasibility of the successful application of natural nanomaterials, such as halloysite nanotubes and nanocellulose, as promising additives to the commercial halogen-free, fire-retardant triphenyl phosphate (TPP) to enhance the flame retardance of open-cell polyurethane foams. The nanocomposite foams were synthesized by in situ polymerization. Investigation of the mechanical properties of the nanocomposite PUF revealed that the nanoscale additives led to a notable decrease in the foam's compressibility. The obtained results of the flammability tests clearly indicate that there is a prominent synergetic effect between the fire-retardant and the natural nanoscale additives. The nanocomposite foams containing a mixture of TPP (10 and 20 parts per hundred polyol by weight) and either 10 wt.% of nanocellulose or 20 wt.% of halloysite demonstrated the lowest burning rate without dripping and were rated as HB materials according to UL 94 classification.
PubMed: 38932089
DOI: 10.3390/polym16121741 -
Polymers Jun 2024The antifungal agent, ketoconazole, and the anti-inflammatory drug, piroxicam, were incorporated into matrices of xanthan or oleic acid-esterified xanthan (Xn) and...
The antifungal agent, ketoconazole, and the anti-inflammatory drug, piroxicam, were incorporated into matrices of xanthan or oleic acid-esterified xanthan (Xn) and polyurethane (PU), to develop topical drug delivery systems. Compared to matrices without bioactive compounds, which only showed a nominal compressive stress of 32.18 kPa (sample xanthan-polyurethane) at a strain of 71.26%, the compressive resilience of the biomaterials increased to nearly 50.04 kPa (sample xanthan-polyurethane-ketoconazole) at a strain of 71.34%. The compressive strength decreased to around 30.67 kPa upon encapsulating a second drug within the xanthan-polyurethane framework (sample xanthan-polyurethane-piroxicam/ketoconazole), while the peak sustainable strain increased to 87.21%. The Weibull model provided the most suitable fit for the drug release kinetics. Unlike the materials based on xanthan-polyurethane, those made with oleic acid-esterified xanthan-polyurethane released the active ingredients more slowly (the release rate constant showed lower values). All the materials demonstrated antimicrobial effectiveness. Furthermore, a higher volume of piroxicam was released from oleic acid-esterified xanthan-polyurethane-piroxicam (64%) as compared to xanthan-polyurethane-piroxicam (44%). Considering these results, materials that include polyurethane and either modified or unmodified xanthan showed promise as topical drug delivery systems for releasing piroxicam and ketoconazole.
PubMed: 38932084
DOI: 10.3390/polym16121734 -
Polymers Jun 2024The 6935M Sprint Quattro Secure S and 6947M Sprint Quattro Secure are high voltage leads designed to administer a maximum of 40 joules of energy for terminating...
The 6935M Sprint Quattro Secure S and 6947M Sprint Quattro Secure are high voltage leads designed to administer a maximum of 40 joules of energy for terminating ventricular tachycardia or ventricular fibrillation. Both leads utilize silicone insulation and a polyurethane outer coating. The inner coil is shielded with polytetrafluoroethylene (PTFE) tubing, while other conductors are enveloped in ethylene tetrafluoroethylene (ETFE), contributing to the structural integrity and functionality of these leads. Polyurethane is a preferred material for the outer insulation of cardiac leads due to its flexibility and biocompatibility, while silicone rubber ensures chemical stability within the body, minimizing inflammatory or rejection responses. Thirteen implantable cardioverter defibrillator (ICD) leads were obtained from the Wright State University Anatomical Gift Program. The as-received devices exhibited varied in vivo implantation durations ranging from less than a month to 89 months, with an average in vivo duration of 41 ± 27 months. Tests were conducted using the Test Resources Q series system, ensuring compliance with ASTM Standard D 1708-02a and ASTM Standard D 412-06a. During testing, a load was applied to the intact lead, with careful inspection for surface defects before each test. Results of load to failure, percentage elongation, percentage elongation at 5 N, ultimate tensile strength, and modulus of elasticity were calculated. The findings revealed no significant differences in these parameters across all in vivo exposure durations. The residual properties of these ICD leads demonstrated remarkable stability and performance over a wide range of in vivo exposure durations, with no statistically significant degradation or performance changes observed.
PubMed: 38932072
DOI: 10.3390/polym16121722 -
Polymers Jun 2024The gyroid structure is a bio-inspired structure that was discovered in butterfly wings. The geometric design of the gyroid structure in butterfly wings offers a unique...
The gyroid structure is a bio-inspired structure that was discovered in butterfly wings. The geometric design of the gyroid structure in butterfly wings offers a unique combination of strength and flexibility. This study investigated sandwich panels consisting of a 3D-printed gyroid structure core and carbon fiber-reinforced polymer (CFRP) facing skin. A filament fused fabrication 3D printer machine was used to print the gyroid cores with three different relative densities, namely 10%, 15%, and 20%. Polylactic acid (PLA) was used as the printing material for the gyroid. The gyroid structure was then sandwiched and joined by an epoxy resin between CFRP laminates. Polyurethane foam (PUF) was filled into the gyroid core to fill the cavity on the core for another set of samples. Flexural and compression tests were performed on the samples to investigate the mechanical behavior of the sandwiches. Moreover, the two-parameter Weibull distribution was used to evaluate the results statistically. As a result, the sandwich-specific facing stress and core shear strength from the three-point bending test of the composites increased with the increase in sandwich density. Core density controls the flexural characteristics of the sandwich. Adding PUF improves the deflection at the maximum stress and the sustained load after fracture of the sandwich. Compression strength, modulus, and energy absorbed by gyroid core sandwiches and their specific properties are higher than the PUF-filled gyroid core sandwiches at equal sandwich density.
PubMed: 38932047
DOI: 10.3390/polym16121698 -
Polymers Jun 2024Recently, clothing development 3D printing and the evaluation of its physical characteristics have been explored. However, few studies have tackled thermal comfort,...
Heat and Moisture Transfer Depending on 3D-Printed Thermoplastic Polyurethane and Ethylene-Vinyl Acetate Foam and the Presence of Holes for 3D Printing Clothing Development.
Recently, clothing development 3D printing and the evaluation of its physical characteristics have been explored. However, few studies have tackled thermal comfort, which is a major contributor to the wearers' comfort. Therefore, this study was designed to suggest effective materials and hole sizes for clothing obtained by 3D printing to maintain a comfortable clothing environment. In particular, two main variables, namely five different materials and three-hole sizes, were analyzed. All samples were placed on a hot plate (36 °C), and their surface temperature and humidity were measured for 10 min. The samples with only thermoplastic polyurethane (TPU) achieved the largest temperature change of 3.2~4.8 °C, whereas those with ethylene-vinyl acetate (EVA) foam exhibited the lowest temperature change of -0.1~2.0 °C. Similarly, the samples with only TPU showed the greatest humidity change of -0.7~-5.5%RH. Moreover, the hole size had a larger effect on humidity change than material type. The samples with large holes achieved the largest humidity change of -4.4%RH, whereas the samples without holes had the smallest humidity change of -1.5%RH after 10 min ( < 0.001). Based on these results, various combinations of materials and hole sizes should be considered to fit the purpose of 3D printing clothing.
PubMed: 38932034
DOI: 10.3390/polym16121684 -
Polymers Jun 2024This research studies natural rubber (NR) composite blends prepared with recycled polyethylene (PE), polyurethane waste (PU), silica (SiO), and aluminum trihydroxide...
Effects of Recycled Polyethylene on Natural Rubber Composite Blends Filled with Aluminum Trihydroxide and Polyurethane Waste: Mechanical and Dynamic Mechanical Properties, Flammability.
This research studies natural rubber (NR) composite blends prepared with recycled polyethylene (PE), polyurethane waste (PU), silica (SiO), and aluminum trihydroxide (ATH) under the proper mixing conditions using an internal mixer and a two-roll mill. The mechanical, impact, dynamic mechanical, and thermal properties, together with flammability, were investigated. NR/PU composites filled with a specific SiO/ATH concentration resulted in excellent flame-retardant properties without using PE. Adding PE causes poor flammability, while using PU and SiO prevents flame extensibility of the composites. In addition, SiO and ATH synergistically improved both mechanical and dynamical mechanical properties. This is attributed to the reinforcement of SiO particles inside the matrix, whereas the ATH releases water as a flame retardant. The V-0 composites tested with UL-94 showed acceptable heat resistance, strength, and durability, making them suitable for interior and exterior applications in buildings without the lightweight requirement.
PubMed: 38932009
DOI: 10.3390/polym16121657 -
Polymers Jun 2024Nowadays, bacteria resistance to many antibiotics is a huge problem, especially in clinics and other parts of the healthcare system. This critical health issue requires...
Phloroglucinol-Based Carbon Quantum Dots/Polyurethane Composite Films: How Structure of Carbon Quantum Dots Affects Antibacterial and Antibiofouling Efficiency of Composite Films.
Nowadays, bacteria resistance to many antibiotics is a huge problem, especially in clinics and other parts of the healthcare system. This critical health issue requires a dynamic approach to produce new types of antibacterial coatings to combat various pathogen microbes. In this research, we prepared a new type of carbon quantum dots based on phloroglucinol using the bottom-up method. Polyurethane composite films were produced using the swell-encapsulation-shrink method. Detailed electrostatic force and viscoelastic microscopy of carbon quantum dots revealed inhomogeneous structure characterized by electron-rich/soft and electron-poor/hard regions. The uncommon photoluminescence spectrum of carbon quantum dots core had a multipeak structure. Several tests confirmed that carbon quantum dots and composite films produced singlet oxygen. Antibacterial and antibiofouling efficiency of composite films was tested on eight bacteria strains and three bacteria biofilms.
PubMed: 38931997
DOI: 10.3390/polym16121646 -
Polymers Jun 2024Recycling flexible polyurethane foam (F-PUF) scraps is difficult due to the material's high cross-linking structure. In this work, a wedge-block-reinforced extruder with...
Recycling flexible polyurethane foam (F-PUF) scraps is difficult due to the material's high cross-linking structure. In this work, a wedge-block-reinforced extruder with a considerable enhanced shear extrusion and stretching area between the rotating screw and the stationary wedge blocks was utilized to recycle F-PUF scraps into powder containing surface-active hydroxyl groups. The powder was then utilized for the quantitative replacement of polyol in the foaming process. Characterizations showed that the continuous shear extrusion and stretching during the extrusion process reduced the volume mean diameter (VMD) of the F-PUF powder obtained by extruding it three times at room temperature to reach 54 μm. The -OH number (OHN) of the powder prepared by extruding it three times reached 19.51 mgKOH/g due to the mechanochemical effect of the powdering method. The F-PUF containing recycled powder used to quantitively replace 10 wt.% polyol was similar in microstructure and chemical structure to the original F-PUF, with a compression set of 2%, indentation load deflection of 21.3 lbf, resilience of 43.4%, air permeability of 815.7 L/m·s, tensile strength of 73.0 Kpa, and tear strength of 2.3 N/cm, indicating that the recycling method has potential for industrial applications.
PubMed: 38931982
DOI: 10.3390/polym16121633 -
Polymers Jun 2024Polymer biocompositions of poly(3-hydroxybutyrate) (P3HB) and linear polyurethanes (PU) with aromatic rings were produced by melt-blending at different P3HB/PU weight...
Polymer biocompositions of poly(3-hydroxybutyrate) (P3HB) and linear polyurethanes (PU) with aromatic rings were produced by melt-blending at different P3HB/PU weight ratios (100/0, 95/5, 90/10, and 85/15). Polyurethanes have been prepared with 4,4'-diphenylmethane diisocyanate and polyethylene glycols with molar masses of 400 g/mol (PU400), 1000g/mol (PU1000), and 1500 g/mol (PU1500). The compatibility and morphology of the obtained polymer blends were determined by infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The effect of the polyurethane content in the biocompositions on their thermal stability and mechanical properties was investigated and compared with those of the native P3HB. It was shown that increasing the PU content in P3HB-PU compositions to 10 wt.% leads to an improvement in the mentioned properties. The obtained results demonstrated that the thermal stability and mechanical properties of P3HB were improved, particularly in terms of increasing the degradation temperature, reducing hardness, and increasing impact strength. The best thermal and mechanical properties were shown by the P3HB-PU polymer compositions containing 10 wt.% of polyurethane modifiers, especially PU1000, which was also confirmed by the morphology analysis of these biocompositions. The presence of polyurethanes in the resulting polymer biocomposites decreases their glass transition temperatures, i.e., makes the materials more flexible. The resulting polymer biocompositions have suitable mechanical properties and thermal properties within the processing conditions for the predicted application as biodegradable, short-lived products for agriculture.
PubMed: 38931968
DOI: 10.3390/polym16121618