Macromol, Volume 2, Issue 2 (June 2022) – 8 articles

Organocatalysis for polymer chemistry has become a subject of significant interest in the last two decades. In this contribution, we have studied the evolution of the microstructure of poly(L-lactide) in solution in toluene at 105 °C in the presence of various organocatalysts. Weak bases such as triethylamine and DMAP (4-dimethylaminopyridine) lead to a low extent of epimerization and a chain scission reaction. The DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) amidine induces in turn important extents of both epimerization (up to 37% D-stereoisomer formation) and chain scission. This has been tentatively attributed to a nucleophilic mechanism. Cinchona alkaloids lead to only a modest amount of epimerization. Phosphazene bases are in turn rather active, especially for high catalytic loadings (>1 mol %). The chain scission observed in this case is proposed to occur via a base-catalyzed hydrolysis mechanism. Finally, it is shown that combining an organic base with an acid can lead to a synergistic effect regarding notably the chain scission reaction. Full article

Due to the hydrodynamic pressure effect, the bearing capacity of the oil film on the surface of a textured friction pair is greater than that of a smooth surface. In this paper, the effects of PTFE surface texture parameters (shape, depth, width, and area ratio) on the oil film bearing capacity and leakage of the sealing system under lubrication are studied using the FLURNT simulation. It is found in this present study that greater texture depths do not necessarily lead to better sealing performance. When the texture depth exceeds a certain level, a reverse flow occurs at the bottom of the texture, thereby weakening the hydrodynamic pressure effect. An optimal texture depth of 5–10 μm maximizes the oil film bearing capacity. Within a certain range, the oil film bearing capacity increases along with texture widths. In addition, leakage of the rectangular texture rises significantly with growing texture widths. Larger texture area ratios result in higher leakage, but the bearing capacity first rises and then falls with an increase in the area ratio, with a maximum value of 70–80%. Considering the influence of texture parameters on oil film bearing capacity and leakage, selecting the most appropriate texture parameters for surface texture treatment optimizes the performance of the sealing system. The findings of this paper provide a theoretical basis for improving the sealing performance of high-end aviation equipment using texture treatment, thereby enabling the application of surface texture technology to improve the tribological properties of materials. Full article

Thermoplastic polyurethane (TPU) is a widely used polymer for a variety of pressure sensing applications because of its softness and shape memory. This work reports the synthesis of novel TPU-based three-dimensional structured (3D) pressure-sensitive composites via the melt mixing method. Poly-methyl methacrylate (PMMA) microbeads of different sizes (5, 10, and 20 µm) were first coated with multi-walled carbon nanotubes (MWCNT) and then incorporated into the TPU matrix for achieving an early electro conductive percolation threshold compared to without PMMA beads. The addition of MWCNT coated PMMA beads reduced the TPU insulated areas by creating a 3D conductive network that finally reflected the early percolation threshold during external pressure. Raman microscopy and XRD results confirmed the MWCNT coated nicely on the surface of PMMA beads. The pressure sensitivity results also confirmed the decrease in resistance of the composites with the increase in the applied external pressure. Composites with 10 µm PMMA bead size showed the most linear responses to the decrease in resistance with increasing pressure and showed a higher strain gauge factor value (3.15) as compared to other composites, which had values of 2.78 and 2.42 for 20 and 5 µm, respectively. Microstructure analysis of the composites by SEM, capacitance, permeability, and thermal conductivity measurements was also investigated to support the above evidence. The results support the suitability of this novel composite as a potential candidate for pressure sensing applications. Full article

In this work, the synthesis and solution self-assembly of partially fluorinated cationic polyelectrolytes based on post-polymerization-modified poly(2-(dimethylamino) ethyl methacrylate), incorporating hydrophobic fluorinated groups along the polymer chain, is reported. The post-polymerization modification aims to establish amphiphilic characteristics and strong polyelectrolyte properties to the polymer. Therefore, the self-organization characteristics in aqueous media are expected to be affected. The poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) homopolymer precursor is synthesized using RAFT polymerization. A quaternization reaction on the amine side groups using heptadecafluoro-10-iododecane results in the poly((2-dimethylamino) ethyl methacrylate-co-quaternized heptadecafluoro-10-iododecane (2-dimethylamino) ethyl methacrylate) (PQFD) amphiphilic statistical copolymers. We intentionally study statistical copolymers in our research of DMAEMA-based polyelectrolytes as there are not many studies about such materials. We have also chosen the incorporation of highly hydrophobic perfluorinated groups to study the changes in the solution properties of the initial hydrophilic homopolymer. The successful synthesis is supported by size-exclusion chromatography (SEC), ¹H-NMR, and FTIR experiments. The self-assembly of the copolymers in aqueous solutions along with the dependence of the properties of the resulting aggregates on the pH, temperature, and ionic strength of the solution are studied using light scattering methods (DLS, ELS) and fluorescence spectroscopy (FS). The structural characteristics of the aggregates depend on composition, solution preparation protocol and solution pH, and temperature. Full article

This study reports the first attempt to employ a potassium–graphite intercalation compound (KC₂₄) as an initiator for the one-pot synthesis of a multi-block copolymer. The results obtained show that KC₂₄ successfully initiated the copolymerization, leading to a copolymer consisting of poly(styrene), poly(methyl methacrylate) and poly(ethylene oxide) blocks. When all three comonomers were introduced simultaneously or in a specific sequence, the resulting copolymers had molecular masses in the range between 170,000 Da and 280,000 Da. Their composition was investigated by size-exclusion chromatography with triple detection (dRI/UV/IR) and ¹H-NMR. The analyses indicated that all copolymers were enriched in methyl methacrylate (50–66 mol%) despite the fact that the comonomers were added in equimolar amounts. Due to the layered structure of the initiator, the polymerization took place in the graphite interlayer spaces and lead to extensive delamination, indicating at the potential to produce in situ graphite/copolymer composite materials. Full article

Polyethylenes (PE) are the most commonly occurring ingredients for post-consumer recyclates (PCR). The structure–property relationships of different types of model PE-based blends are established using multiple thermo-rheological analyses. Although considered “simple”, the complex behavior of model PE-based blends is experimentally demonstrated for the first time for metallocene-catalyzed, linear, low-density polyethylenes (mLLDPE) with different microstructures that are commonly encountered in PCR. During non-isothermal crystallization, the microstructure of mLLDPE predominantly influences the interaction between mLLDPE and LDPE. Based on the mLLDPE microstructure, the molten LDPE phase acts either as a nucleating agent or as a crystallization rate promoting agent. Both rheological and thermal analyses show that higher activation energy is required for the reptation or movement of polymer chains in a highly branched microstructure with long chain branching (LCB) compared to a linear microstructure with short chain branching (SCB). The quasi-melt response, as measured by thermal analysis under non-isothermal conditions, is distinctly different and sensitive to both the SCB and LCB present in the LLDPE/LDPE blends. Full article

The automotive sector covers almost 40% of polyamide (PA) total demand. A suitable solution to improve the sustainability of this sector is the exploitation of PA matrices sourced from renewable origins, such as PA11, and their reinforcement with natural fibers such as vegetable flax and mineral basalt. A preliminary study on the quasi-static properties of PA11-based composites reinforced with an intraply flax/basalt hybrid fabric demonstrated their feasibility for semi-structural purposes in the transportation field, but their application needs to be validated against dynamic loading. In this regard, this work investigated the low-velocity impact performance of PA11 flax/basalt hybrid composites (10 J, 20 J and 30 J) as a function of temperature (room temperature and +80 °C) and plasticizer addition (butyl-benzene-sulfonamide). The results proved that plasticized PA11 is endowed with a lower glass transition temperature (~15 °C, from DMA) and melting temperature (~10 °C, from DSC), which simplifies manufacturing and processing, but also possesses a higher toughness which delays penetration phenomena and reduces permanent indentation at room temperature between 20.5% and 42.8% depending on impact energy. The occurrence of matrix plasticization at +80 °C caused a more flexible and tougher response from the laminates with a decrease in linear stiffness and a delay in penetration phenomena which made the plasticizer effect less prominent. Full article

This research presents a new approach to the dispersion and stabilization of gold nanoparticles from aqueous to organic solution through the use of alkylsilanes. The unique phase activity of poly(hydro)silanes inspired the investigation of monomeric hydrosilanes as transfer agents. This method utilizes n-butylsilane, hexylsilane, octylsilane, and octadecylsilane as transfer agents to complete a ligand exchange, allowing the nanoparticles to flow into organic solution. These reactions were monitored and characterized through UV-Vis Spectrometry (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), and Transmission Electron Microscopy (TEM). The gold and silver nanoparticles transferred using this protocol maintained their size and shape throughout the reaction. This phase-transfer reaction successfully transferred 2-AST stabilized gold and silver nanoparticles to a variety of organic solvents which remained stable for prolonged periods. Full article