Polymers, Volume 12; doi:10.3390/polym12040854
The aim of this contribution was to evaluate the impact of processing methods and polymeric carriers on the physicochemical properties of solid dispersions of the poorly soluble drug progesterone (PG). Five polymers: hydroxypropyl methylcellulose (HPMC), hydroxypropyl methylcellulose acetate succinate (HPMCAS), microcrystalline cellulose (MCC), polyvinylpyrrolidone (PVP) and silica (SiO2), and two processing methods: solvent evaporation (SE) and mechano-chemical activation by co-milling (BM) were applied. H-bonding was demonstrated by FTIR spectra as clear shifting of drug peaks at 1707 cm−1 (C20 carbonyl) and 1668 cm−1 (C3 carbonyl). Additionally, spectroscopic and thermal analysis revealed the presence of unstable PG II polymorphic form and a second heating DSC cycle, the presence of another polymorph possibly assigned to form III, but their influence on drug solubility was not apparent. Except for PG–MCC, solid dispersions improved drug solubility compared to physical mixtures. For SE dispersions, an inverse relationship was found between drug water solubility and drug–polymer Hansen solubility parameter difference (Δδt), whereas for BM dispersions, the solubility was influenced by both the intermolecular interactions and the polymer Tg. Solubility improvement with SE was demonstrated for all except PG–MCC dispersions, whereas improvement with BM was demonstrated by the PG–HPMC, PG–PVP and PG–HPMCAS dispersions, the last showing impressive increase from 34.21 to 82.13 μg/mL. The extensive H-bonding between PG and HPMCAS was proved by FTIR analysis of the dispersion in the liquid state. In conclusion, although SE improved drug solubility, BM gave more than twice greater improvement. This indicates that directly operating intermolecular forces are more efficient than the solvent mediated.
Polymers, Volume 12; doi:10.3390/polym12040851
Recycled newspaper (NP)/high density polyethylene (HDPE) laminated composite can reach the physical and mechanical criteria for most industrial applications, which shows the potential of using solid-state waste paper in engineering materials. Herein, the effects of splicing pattern and size on the physical and mechanical properties of the laminated composite were investigated with the ultimate purpose to fabricate a large-scaleale composite. The laminated composite with a stair-like splicing had better physical and mechanical properties than that with a vertical splicing. An efficient stress transfer could be guaranteed when the distance between the two adjacent junctions were greater than a critical proportion of 1/32 of the length at longitudinal direction. The tensile and flexural properties of the large-scaleale composite with a stair-like splicing, which was fabricated at the splicing ratio of 1/32, were 109 ± 4.2 MPa (MOR), 9836 ± 411 MPa (MOE), 119 ± 7.1 MPa (MOR) and 10002 MPa ± 347 (MOE).
Polymers, Volume 12; doi:10.3390/polym12040855
When processing particular polymers, it may be necessary to increase the molecular weight, for example, during polymer recycling or foaming. Chemical additives such as chain extenders (CE) are often used to build up the molecular weight during reactive extrusion. One issue of chain extenders, however, is that they can cause gelation or crosslinking of the polymer during processes with long residence times. This can lead to strong process fluctuations, undesired process shutdowns due to uncontrollable torque and pressure fluctuations and finally consistent material quality cannot be guaranteed. To measure and understand the reactivity between the polymer and the CE a rheological test can help. However, the standard gel point evaluation used for thermosets by examining the point of intersection of storage- and loss modules is not suitable, as this method is frequency-dependent. This study uses a multiwave rheology test to identify the gel-point more reliably. Both evaluation methods were compared on a polyamide 12 system, which is modified with an industrially relevant chain extender. The results show that the multiwave test can be applied on a chemical modified thermoplastic system and that the material system indicates a general tendency to crosslink. The frequency-independent gel-point evaluation shows that the gel-point itself is dependent on the processing temperature. Finally, it was possible to detect undesired side reactions, which are not recognizable with the standard testing method. Both findings are directly relevant for the reactive extrusion process and help to understand the mechanism of gelation.
Polymers, Volume 12; doi:10.3390/polym12040845
The biostability of the polyurethanes Tecoflex EG-80A and Pellethane 2363-80A, used as basic polymers of the vascular grafts (VGs) produced by electrospinning, as well as the tensile strength of Tecoflex VGs, are studied. Solutions of Tecoflex or Pellethane with gelatin and bivalirudin in 1,1,1,3,3,3-hexafluoroisopropanol are used for VG production. After 1, 12, and 24 weeks of VG implantation in the infrarenal position of the abdominal aorta of Wistar rats, VGs are explanted, fixed in formalin, freed from outer tissues, dialyzed, and dried. The polyurethanes are extracted from VGs by dispersion/extraction in tetrahydrofuran (THF) and freed from the excess of THF-insoluble biopolymers. The stability of polyurethanes is assessed by IR spectroscopy and gel permeation chromatography. Pellethane has emerged to be stable at all experimental points. Tecoflex loses approximately 10% of its molecular weight (both Mn and Mw) after 3 months and restored its initial value within 6 months of its functioning as a graft. Mechanical testing demonstrates a 30% reduction in the tensile strength after 3 months in VG and a 10% increase after 6 months. The stability and mechanical properties of polyurethane-based VGs demonstrate their utility for the reconstitution of damaged arteries.
Polymers, Volume 12; doi:10.3390/polym12040856
In this article we report an easy synthetic route towards hyperbranched polyglycerols (Amm-HBPGs) containing trimethylammonium groups and siloxane or hydroxyl end-groups. Siloxane derivatives of Amm-HBPGs were synthesized in an efficient five-step procedure including an anionic ring opening copolymerization of the phthalimide-epoxy monomer with glycidol, followed by reactions with allyl bromide, hydrosililation with hydrogenheptamethyltrisiloxane, hydrazinolysis of phthalimide groups and quaternization of resulting amine groups with methyl iodide. Hydroxyl derivatives were obtained by quaternization of previously reported aminated HBPG’s with methyl iodide. Polymeric products were characterized using various NMR techniques, FTIR, and elemental analysis. Both Amm-HBPGs were shown to be effective in catalysis of addition of CO2 to oxirane. The hydrophilic catalysts showed higher efficiency but synthesis of ethylene carbonate was accompanied by formation of small amounts of ethylene glycol. The siloxane-containing catalyst was easily separable from reaction mixture showing high potential in the process of converting carbon dioxide into valuable chemical raw materials.
Polymers, Volume 12; doi:10.3390/polym12040832
In this article, the effect of polyallylamine (PAA) on the structure and catalytic characteristics of alcohol dehydrogenase (ADH) was studied. For this research, we used methods of stationary kinetics and fluorescence spectroscopy. It has been shown that PAA non-competitively inhibits ADH activity while preserving its quaternary structure. It was established that 0.1 M ammonium sulfate removes the inhibitory effect of PAA on ADH, which is explained by the binding of sulfate anion (NH4)2SO4 with polyallylamine amino groups. As a result, the rigidity of the polymer chain increases and the ability to bind to the active loop of the enzyme increases. It is also shown that sodium chloride removes the inhibitory effect of PAA on ADH due to an electrostatic screening of the enzyme from polyelectrolyte. The method of encapsulating ADH in polyelectrolyte microcapsules was adapted to the structure and properties of the enzyme molecule. It was found that the best for ADH is its encapsulation by adsorption into microcapsules already formed on CaCO3 particles. It was shown that the affinity constant of encapsulated alcohol dehydrogenase to the substrate is 1.7 times lower than that of the native enzyme. When studying the affinity constant of ADH in a complex with PAA to ethanol, the effect of noncompetitive inhibition of the enzyme by polyelectrolyte was observed.
Polymers, Volume 12; doi:10.3390/polym12040833
Highly hydrophobic cotton fabrics were obtained with poly(methylhydrogen)siloxane (PMHS) and a further fluorinated olefin modification. The chemical structures and microstructures of PMHS-modified cotton fabrics were characterized, and application of the resultant cotton fabrics in stain resistance and oil–water separation was demonstrated. PMHS chains with very low surface energy were grafted onto cotton fabric by the dehydrogenation reaction between –Si–H of PMHS and –OH groups of cotton fabric at room temperature. The water contact angle of PMHS-modified cotton fabric was 141.7°, which provided the modified cotton fabric with good stain resistance to waterborne pollutants. The separation efficiency of diesel from water was higher than 92% for 20 repeatable separation cycles. A further improvement in stain resistance to oil was also demonstrated by a further addition reaction of 1H,1H,2H-perfluoro-1-decene with PMHS-modified cotton fabric.
Polymers, Volume 12; doi:10.3390/polym12040834
Waterlogged archaeological wood (WAW) artifacts, made of natural biodegradable polymers, are important parts of many precious cultural heritages. It is of great importance to understand the hygroscopic behavior of WAW in different deterioration states for the development of optimal drying processes and choices of safe storage in varying conditions. This was investigated in a case-study using two Hopea (Giam) and two Tectona (Teak) WAW samples collected from the Xiaobaijiao No.1 shipwreck. The deterioration state of WAW was evaluated by the maximum water content (MWC) method and by the cell morphological structure. Both Hopea and Tectona WAW could be classified into moderately and less decayed WAW. The hygroscopic behavior of moderately and less decayed WAW was then comparatively investigated using Dynamic Vapor Sorption (DVS) measurements alongside two sorption fitting models. Compositional analysis and hydroxyl accessibility measurements of WAW cell walls were shown to correlate with the hygroscopicity of WAW in different deterioration states. It was concluded that moderately decayed WAW possessed higher hygroscopicity and hysteresis than less decayed WAW because of the lower relative content of polysaccharides and the higher relative content of lignin, including the slow hydrolysis of O-acetyl groups of xylan and the partial breakage of β-O-4 interlinks, accompanied by an increased hydroxyl accessibility. This work helps in deciding on which consolidation measures are advised for shipwreck restauration, i.e., pretreatments with specific consolidates during wood drying, particularly for wooden artifacts displayed in museums.
Polymers, Volume 12; doi:10.3390/polym12040835
Polyester-based biocomposites containing INZEA F2® biopolymer and almond shell powder (ASP) at 10 and 25 wt % contents with and without two different compatibilizers, maleinized linseed oil and Joncryl ADR 4400®, were prepared by melt blending in an extruder, followed by injection molding. The effect of fine (125–250 m) and coarse (500–1000 m) milling sizes of ASP was also evaluated. An improvement in elastic modulus was observed with the addition of< both fine and coarse ASP at 25 wt %. The addition of maleinized linseed oil and Joncryl ADR 4400 produced some compatibilizing effect at low filler contents while biocomposites with a higher amount of ASP still presented some gaps at the interface by field emission scanning electron microscopy. Some decrease in thermal stability was shown which was related to the relatively low thermal stability and disintegration of the lignocellulosic filler. The added modifiers provided some enhanced thermal resistance to the final biocomposites. Thermal analysis by differential scanning calorimetry and thermogravimetric analysis suggested the presence of two different polyesters in the polymer matrix, with one of them showing full disintegration after 28 and 90 days for biocomposites containing 25 and 10 wt %, respectively, under composting conditions. The developed biocomposites have been shown to be potential polyester-based matrices for use as compostable materials at high filler contents.
Polymers, Volume 12; doi:10.3390/polym12040836
Waterproof-breathable (WB) materials with outstanding waterproofness, breathability, and mechanical performance are critical in diverse consumer applications. Electrospun nanofibrous membranes with thin fiber diameters, small pore sizes, and high porosity have attracted significant attention in the WB fabric field. Hot-press treatment technology can induce the formation of inter-fiber fusion structures and hence improve the waterproofness and mechanical performance. By combining electrospinning and hot-press treatment technology, polyurethane/fluorinated polyurethane/thermoplastic polyurethane/alkylsilane-functionalized graphene (PU/FPU/TPU/FG) nanofiber WB fabric was fabricated. Subsequently, the morphologies, porous structure, hydrostatic pressure, water vapor transmission rate (WVTR), and stress–strain behavior of the nanofiber WB fabric were systematically investigated. The introduction of the hydrophobic FG sheet structure and the formation of the inter-fiber fusion structure greatly improved not only the waterproofness but also the mechanical performance of the nanofiber WB fabric. The optimized PU/FPU/TPU-50/FG-1.5 WB fabric exhibited an excellent comprehensive performance: a high hydrostatic pressure of 80.4 kPa, a modest WVTR of 7.6 kg m−2 d−1, and a robust tensile stress of 127.59 MPa, which could be used to achieve various applications. This work not only highlights the preparation of materials, but also provides a high-performance nanofiber WB fabric with huge potential application prospects in various fields.