Influence of the Type of Soft Segment on the Selected Properties of Polyurethane Materials for Biomedical Applications.

This work presents the synthesis and characterization of new TPUs obtained by melt polyaddition using 1,1'-methanediylbis(4-isocyanatocyclohexane) (HMDI, Desmodur W®), a new unconventional chain extender, i.e., (methanediyldibenze-ne-4,1-diyl)dimethanediol, and five types of soft segments differing in structure and molar masses. The structure of the obtained polymers was determined (by using the Fourier transform infrared spectroscopy and X-ray diffraction methods), and the physicochemical (reduced viscosity, density), optical (UV-VIS), processing (MFR) and thermal (DSC and TGA-FTIR) as well as surface, antibacterial and cytotoxic properties were determined. Based on the results obtained, it can be stated that the type of soft segment used significantly affects the properties of the obtained polymers. The most favorable properties for use in medicine were demonstrated by materials based on a polycarbonate soft segment.

Luminescent Hybrid BPA.DA-NVP@Eu2L3 Materials: In Situ Synthesis, Spectroscopic, Thermal, and Mechanical Characterization.

A series of homogeneous hybrid BPA.DA-NVP@Eu2L3 materials were obtained through an in situ approach where the luminescent dopant was formed at the molecular level with different contents (0.1; 0.2; 0.5; 1; and 2% by weight). A Europium(III) complex (Eu2L3) with quinoline-2,4-dicarboxylic acid was applied as a luminescence additive while a polymer matrix consisted of a combination of bisphenol A diacrylate (BPA.DA) and N-vinylpyrrolidone (NVP) monomers. Synthesis steps and the final materials were monitored by NMR and Fourier transform infrared spectroscopy (FTIR). The emission, excitation spectra, lifetime, and quantum yield measurements were applied for the determination of the photophysical characteristics. The thermal and mechanical properties of the obtained materials were tested via thermal analysis methods (TG/DTG/DSC and TG-FTIR) in air and nitrogen atmospheres, dynamic mechanical analysis (DMA), and hardness and bending measurements. Generally, even a small addition of the metal complex component causes changes in the thermal, mechanical, and luminescent properties. Hybrid materials with a greater europium complex content are characterized by a lower stiffness and hardness while the heterogeneity and the flexibility of the samples increase. A very small amount of an Eu2L3 admixture (0.1% wt.) in a hybrid material causes an emission in the red spectral range and the luminescence intensity was reached for the BPA-DA-NVP@1%Eu2L3 material. These materials may be potentially used in chemical sensing, security systems, and protective coatings against UV.

Preparation and Thermo-Mechanical Characteristics of Composites Based on Epoxy Resin with Kaolinite and Clinoptilolite.

Herein the synthesis, characterization, and study of spectroscopic, thermal, and thermo-mechanical properties of polymeric composites are presented. The composites were obtained in special molds (8 × 10 cm) based on the commercially available epoxy resin Epidian® 601 cross-linked by 10% w/w triethylenetetramine (TETA). To improve the thermal and mechanical properties of the synthetic epoxy resins, natural fillers in the form of minerals from the silicate cluster kaolinite (KA) or clinoptilolite (CL) were added to the composites. The structures of the materials obtained were confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR/FTIR). The thermal properties of the resins were investigated by differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA) in an inert atmosphere. The hardness of the crosslinked products was determined using the Shore D method. Moreover, strength tests were performed on the 3PB (three-point bending) specimen, with the analysis of tensile strains conducted using the Digital Image Correlation (DIC) technique.

Special Issue: Synthesis, Processing, Structure and Properties of Polymer Materials.

Polymeric materials are widely used in many different technical fields [...].

New Segmented Poly(Thiourethane-Urethane)s Based on Poly(ε-Caprolactone)Diol Soft Segment: Synthesis and Characterization.

New segmented poly(thiourethane-urethane)s (SPTURs) were synthesized by the reaction of 1,1'-methanediylbis (4-isocyanatocyclohexane) (Desmodur W®, HMDI) and poly(ε-caprolactone)diol (PCL) and (methanediyldibenzene-4,1-diyl)dimethanethiol as nonconventional polymer chain extender. FTIR spectroscopy was used for the structural analysis of obtained polymers. The molecular weight distribution was examined by GPC chromatography. Based on the measured contact angles, free surface energy parameters were calculated. Thermal properties of polymers were examined by DSC and TGA, while viscoelastic properties were measured by DMTA. The tensile, adhesive and optical properties were also investigated for the obtained polymers. It was shown that SPTURs were transparent or partially transparent solids with high molar masses up to 84,300 Da. These polymers showed a good resistance to hydrolysis during incubation in Optylite® physiological saline over 8 weeks. Obtained polymers possessed a tensile strength of up to 43.26 MPa, hardness of up to 96.25/59.00 Sh A/D and adhesion to copper of 14.66 MPa. The surface properties of the obtained polymers show that all obtained SPTURs were hydrophilic (CAs for water between 64.07° and 73.12°) with calculated SFE up to 46.69 mN/m.

Synthesis and Characterization of New Polycarbonate-Based Poly(thiourethane-urethane)s.

The new segmented poly(thiourethane-urethane)s (PTURs) based on 1,1'-methanediylbis(4-isocyanatocyclohexane) (HMDI, Desmodur W®), polycarbonate diol (PCD, Desmophen C2200) and (methanediyldibenzene-4,1-diyl)dimethanethiol were synthesized by one-step melt polyaddition method. The obtained PTURs, with a content of 30-60 wt% of the hard segments (HS), were tested in which the influence of changes in the HS content on their properties was determined. The polymers were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), thermal analysis (DSC, TGA) and thermomechanical analysis (DMTA). Additionally, tensile strength, optical (refractive index, UV-VIS and color) and surface properties of the obtained polymers (contact angle and surface free energy) and adhesion to copper were examined. FTIR analysis verified the supposed structure of the polymers obtained and showed a complete conversion of the isocyanate groups. TGA analysis confirmed the relatively good thermal stability of the polymers. On the other hand, after performing the DSC analysis, it was possible to state that the obtained materials were partially or completely amorphous, and the microphase separation decreased with increasing HS content in the polymer. Similar observations were made from the DMTA data. In addition, the hardness, tensile strength, modulus of elasticity, storage modulus, adhesion to copper, refractive index and total free surface energy increased with increasing HS content in the polymer.

Investigation of Degradation of Composites Based on Unsaturated Polyester Resin and Vinyl Ester Resin.

This study compares the degradation process of unsaturated polyester resin (UPR) and vinyl ester resin (VER) and their biocomposites with kraft lignin. In order to study their degradation, accelerated aging, immersion in different solvents, microwave radiation and high temperature were applied. The results show that, depending on the conditions, the degradation assumes a different course. The VER resin is more chemically resistant than the UPR resin. In the case of the composites immersed in an aggressive solvent (acetone), it can be observed that the polymer matrix is degraded, whereas in water only a small increase of weight takes place. Immersion in NaOH initiates the degradation process consisting in the hydrolysis of ester bonds, which are especially observed for pure resins. Under the influence of UV radiation and microwaves, the resins are additionally cross-linked. Thermogravimetric analysis shows that in the case of composites heated to 1000 °C, a residual mass remains, which is carbonized with lignin. In turn, composites treated with microwaves lost weight.

Synthesis and Spectroscopic Analyses of New Polycarbonates Based on Bisphenol A-Free Components.

This paper discusses a new synthesis of bisphenol A-free polycarbonates based on four aliphatic-aromatic systems. In the first stage, different types of monomers (with/without sulfur) derived from diphenylmethane were synthesized. Then, new polycarbonates were prepared in the reactions with diphenyl carbonate (DPC) by transesterification and polycondensation reactions. Three different catalysts (zinc acetate, 4-(dimethylamino)pyridine and benzyltriethylammonium chloride) were tested. The structures of the compounds were confirmed by Nuclear Molecular Resonance spectroscopy (NMR) in each stage. The chemical structures of the obtained polycarbonates were verified by means of Attenuated Total Reflectance Fourier Transform infrared spectroscopy (ATR-FTIR). The presence of a carbonyl group in the infrared spectrum confirmed polycarbonate formation. Thermal studies by differential scanning calorimetry (DSC) were carried out to determine the melting temperatures of the monomers. A gel permeation chromatography analysis (GPC) of the polycarbonates was performed in order to investigate their molar masses. Thermal analysis proved the purity of the obtained monomers; the curves showed a characteristic signal of melting. The obtained polycarbonates were characterized as having high resistance to organic solvents, including tetrahydrofuran. The GPC analysis proved their relatively large molar masses and their low dispersity.

Effect of Eco-Friendly Peanut Shell Powder on the Chemical Resistance, Physical, Thermal, and Thermomechanical Properties of Unsaturated Polyester Resin Composites.

The paper investigates the synthesis of eco-friendly composites and their properties before and after immersion in solvents of different chemical natures. For their preparation, unsaturated polyester resin (UPR) based on recycled poly (ethylene terephthalate) (PET) and peanut shell powder (PSP) were used. Polymerization was carried out in the presence of environmentally friendly polymeric cobalt. Distilled water, acetone, 10% hydrochloric acid, 40% sodium hydroxide, toluene, and 2% sodium carbonate were used as solvents in the chemical resistance test. Changes in the structure, properties, and appearance (morphology) of composites after 140 days of immersion in solvents were investigated. The results show that both the resin and its composites show resistance towards 10% HCl and toluene. The immersion in water has no significant effect on the resin, but for PSP composites, the plasticizing effect of water was observed. In acetone, after only one day, the resin and its composite with 10% PSP shrink and fall into pieces. However, the most destructive is an alkaline environment. After the immersion test, a huge increase in mass and a deterioration of gloss and thermomechanical properties were observed. The destructive influence of the 40% NaOH environment mainly concerned the resin.

Biodegradation of Different Types of Plastics by Tenebrio molitor Insect.

Looking for new, sustainable ways to utilize plastics is still a very pertinent topic considering the amount of plastics produced in the world. One of the newest and intriguing possibility is the use of insects in biodegradation of plastics, which can be named entomoremediation. The aim of this work was to demonstrate the ability of the insect Tenebrio molitor to biodegrade different, real plastic waste. The types of plastic waste used were: remains of thermal building insulation polystyrene foam (PS), two types of polyurethane (kitchen sponge as PU1 and commercial thermal insulation foam as PU2), and polyethylene foam (PE), which has been used as packaging material. After 58 days, the efficiency of mass reduction for all of the investigated plastics was 46.5%, 41.0%, 53.2%, and 69.7% for PS, PU1, PU2, and PE, respectively (with a dose of 0.0052 g of each plastic per 1 mealworm larvae). Both larvae and imago were active plastic eaters. However, in order to shorten the duration of the experiment and increase the specific consumption rate, the two forms of the insect should not be combined together in one container.

New lignin-based hybrid materials as functional additives for polymer biocomposites: From design to application.

Within this study, the ZrO2/lignin and ZrO2-SiO2/lignin hybrid materials were obtained for the first time. The mechanical grinding method was used for this purpose. In order to determine the properties of obtained lignin-based hybrids and the components used to produce them, as well as to evaluate the efficiency of their preparation, the authors used such research techniques as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, porous structure analysis and thermal stability assessment (TGA/DTG). The next step involved using the components and produced hybrid materials as polymer fillers for poly(methyl methacrylate) (PMMA). The obtained lignin-based hybrid biocomposites have then been thoroughly characterized using gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and hardness testing. All the conducted tests confirm the possibility of using the obtained bio-based products in practice, within the widely understood construction industry, for producing durable building facades or noise barriers, among others.

Modern Biodegradable Plastics-Processing and Properties Part II.

Four different plastics were tested: potato starch based plastic (TPS-P)-BIOPLAST GF 106/02; corn starch based plastic (TPS-C)-BioComp BF 01HP; polylactic acid (polylactide) plastic (PLA)-BioComp BF 7210 and low density polyethylene, trade name Malen E FABS 23-D022; as a petrochemical reference sample. Using the blown film extrusion method and various screw rotational speeds, films were obtained and tested, as a result of which the following were determined: breaking stress, strain at break, static and dynamic friction coefficient of film in longitudinal and transverse direction, puncture resistance and strain at break, color, brightness and gloss of film, surface roughness, barrier properties and microstructure. The biodegradable plastics tested are characterized by comparable or even better mechanical strength than petrochemical polyethylene for the range of film blowing processing parameters used here. The effect of the screw rotational speed on the mechanical characteristics of the films obtained was also demonstrated. With the increase in the screw rotational speed, the decrease of barrier properties was also observed. No correlation between roughness and permeability of gases and water vapor was shown. It was indicated that biodegradable plastics might be competitive for conventional petrochemical materials used in film blowing niche applications where cost, recyclability, optical and water vapor barrier properties are not critical.

Preparation, Thermal, and Thermo-Mechanical Characterization of Polymeric Blends Based on Di(meth)acrylate Monomers.

This study presents the preparation and the thermo-mechanical characteristics of polymeric blends based on di(meth)acrylates monomers. Bisphenol A glycerolate diacrylate (BPA.GDA) or ethylene glycol dimethacrylate (EGDMA) were used as crosslinking monomers. Methyl methacrylate (MMA) was used as an active solvent in both copolymerization approaches. Commercial polycarbonate (PC) was used as a modifying soluble additive. The preparation of blends and method of polymerization by using UV initiator (Irqacure® 651) was proposed. Two parallel sets of MMA-based materials were obtained. The first included more harmless linear hydrocarbons (EGDMA + MMA), whereas the second included the usually used aromatic copolymers (BPA.GDA + MMA). The influence of different amounts of PC on the physicochemical properties was discussed in detail. Chemical structures of the copolymers were confirmed by attenuated total reflection-Fourier transform infrared (ATR/FT-IR) spectroscopy. Thermo-mechanical properties of the synthesized materials were investigated by means of differential scanning calorimetry (DSC), thermogravimetric (TG/DTG) analyses, and dynamic mechanical analysis (DMA). The hardness of the obtained materials was also tested. In order to evaluate the surface of the materials, their images were obtained with the use of atomic force microscopy (AFM).

Synthesis, Characterization and Testing of Antimicrobial Activity of Composites of Unsaturated Polyester Resins with Wood Flour and Silver Nanoparticles.

This paper presents the properties of the wood-resin composites. For improving their antibacterial character, silver nanoparticles were incorporated into their structures. The properties of the obtained materials were analyzed in vitro for their anti-biofilm potency in contact with aerobic Gram-positive Staphylococcus aureus and Staphylococcus epidermidis; and aerobic Gram-negative Escherichia coli and Pseudomonas aeruginosa. These pathogens are responsible for various infections, including those associated with healthcare. The effect of silver nanoparticles incorporation on mechanical and thermomechanical properties as well as gloss were investigated for the samples of composites before and after accelerating aging tests. The results show that bacteria can colonize in various wrinkles and cracks on the composites with wood flour but also the surface of the cross-linked unsaturated polyester resin. The addition of nanosilver causes the death of bacteria. It also positively influences mechanical and thermomechanical properties as well as gloss of the resin.

Green Composites Based on Unsaturated Polyester Resin from Recycled Poly(Ethylene Terephthalate) with Wood Flour as Filler-Synthesis, Characterization and Aging Effect.

The paper investigates the synthesis of green composites and their properties before and after the laboratory accelerated aging tests. Materials were made of unsaturated polyester resins (UPRs) based on recycled poly(ethylene terephthalate) (PET) and wood flour (WF). The effect of dibenzylideneacetone (dba) addition on mechanical and thermomechanical properties was also determined. Green composites were obtained using environment friendly polymeric cobalt as an accelerator. Before and after exposition to the xenon lamp radiation, the UPRs physically modified by WF were characterized only by a greater flexural modulus compared with the analogous composites based on the pure resin. Addition of dba caused the increase of flexural modulus, flexural strength, strain at break and mechanical loss factor compared to the non-modified material. After aging only the last mentioned parameter took on lower values compared to the pure resin analogues.

Modern Biodegradable Plastics-Processing and Properties: Part I.

This paper presents a characterization of a plastic extrusion process and the selected properties of three biodegradable plastic types, in comparison with LDPE (low-density polyethylene). The four plastics include: LDPE, commercial name Malen E FABS 23-D022; potato starch based plastic (TPS-P), BIOPLAST GF 106/02; corn starch based plastic (TPS-C), BioComp®BF 01HP; and a polylactic acid (polylactide) plastic (PLA), BioComp®BF 7210. Plastic films with determined geometric parameters (thickness of the foil layer and width of the flattened foil sleeve) were produced from these materials (at individually defined processing temperatures), using blown film extrusion, by applying different extrusion screw speeds. The produced plastic films were tested to determine the geometrical features, MFR (melt flow rate), blow-up ratio, draw down ratio, mass flow rate, and exit velocity. The tests were complemented by thermogravimetry, differential scanning calorimetry, and chemical structure analysis. It was found that the biodegradable films were extruded at higher rate and mass flow rate than LDPE; the lowest thermal stability was ascertained for the film samples extruded from TPS-C and TPS-P, and that all tested biodegradable plastics contained polyethylene.

Polyethylene-Matrix Composites with Halloysite Nanotubes with Enhanced Physical/Thermal Properties.

The aim of the present work is to investigate the effect of halloysite nanotubes (HNT) on the mechanical properties of low-density polyethylene composites modified by maleic anhydride-grafted PE (PE-graft-MA). Polyethylene nanocomposites were prepared using an injection molding machine, Arburg Allrounder 320 C 500-170; the HNT content was varied at 0 wt %, 2 wt %, 4 wt % and 6 wt %, and the PE-graft-MA content was varied at 5 wt %. The composites were examined for their ultimate tensile stress, strain at ultimate stress, hardness, impact strength, melt flow rate, heat deflection temperature, Vicat softening temperature, crystallinity degree and phase transition temperature. It was found that the addition of halloysite nanotubes to low-density polyethylene (LDPE) led to an increased heat deflection temperature (HDT, up to 47 °C) and ultimate tensile strength (up to 16.00 MPa) while the Vicat softening temperature, strain at ultimate stress, impact strength and hardness of examined specimens slightly decreased. Processing properties of the materials specified by the melt flow rate (MFR) deteriorated almost twice. The results have demonstrated that the nanoparticles can reinforce enhance LDPE at low filler content without any considerable loss of its ductility, but only when halloysite nanotubes are superbly distributed in the polyethylene matrix.

Thermal and Mechanical Behavior of New Transparent Thermoplastic Polyurethane Elastomers Derived from Cycloaliphatic Diisocyanate.

New transparent thermoplastic polyurethane elastomers (TPURs) with the hard-segment content of ≈50 mass % were synthesized by one-step melt polyaddition of 1,1'-methanediylbis(4-isocyanatocyclohexane), 2,2'-methylenebis[(4,1-phenylene)-methylenesulfanediyl]diethanol (diol E), 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid (DMPA), a poly(oxytetramethylene) diol of M ¯ n = 1000 g/mol (PTMO), or a poly(hexametylene carbonate) diol of M ¯ n = 860 g/mol (PHCD). Herein, I prepared TPURs in which 20, 40, and 60 mol % of diol E was replaced with DMPA, an ionic chain extender. The structure of polymers was examined by ATR-FTIR. Their thermal and mechanical behaviors were determined by means of thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile tests, and Shore A/D hardness. Their optical properties are described. Generally, the addition of carboxyl groups to the polymer resulted in decreases in their thermal stability, transparency, and refractive indexes. Furthermore, the use of different soft segments revealed significant differences in both mechanical and thermal properties of the polymers obtained.

New thermoplastic poly(carbonate-urethane)s based on chain extenders with sulfur atoms.

New thermoplastic segmented polyurethanes were obtained by a one-step melt polyaddition using 40, 50 and 60 mol% poly(hexane-1,6-diyl carbonate) diol of [Formula: see text] g mol-1, 1,1'-methanediylbis(4-isocyanatobenzene) and 2,2'-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol, 2,2'-[oxybis(benzene-1,4-diylsulfanediyl)]diethanol or 2,2'-[sulfanediylbis(benzene-1,4-diylsulfanediyl)]diethanol as a chain extender. FTIR, atomic force microscopy, differential scanning calorimetry and thermogravimetry were used to examine the polyurethanes' structure and thermal properties. Moreover, their Shore A/D hardness, tensile, adhesive and optical attributes were determined. They were transparent high-molar-mass materials showing good tensile strength (up to 51.9 MPa). The polyurethanes exhibited improved adhesion to copper taking into consideration that of conventional ones, and middle or high refractive index values (1.57-1.60), and both these parameters increased with an increase of the content of sulfur atoms in the polyurethane chain. The newly obtained polyurethanes can be considered as materials for numerous medical and optical appliances.