Search Results (12)

The present research describes the chemical composition and the enantiomeric profile of a spicy green aroma essential oil, distilled from the dry leaves of Baccharis sinuata Kunth (Asteraceae). The distillation yield was as high as 3.0% by weight. The chemical analysis was conducted on two columns, coated with stationary phases of different polarity (5% phenyl—95% methyl polysiloxane, expressed by weight, and 100% polyethylene glycol). Major components (≥2.0% as an average value between the two columns) were as follows: β-pinene (4.9%), limonene (39.0%), (E)-β-caryophyllene (2.0%), bicyclogermacrene (2.7%), γ-cadinene (4.0%), δ-cadinene (7.3%), β-eudesmol (2.0%), α-eudesmol (3.0%), and α-cadinol (2.0%). For the enantioselective analysis, 10 enantiomeric pairs were investigated, using two capillary columns coated with different chiral selectors. As a result, (1R,5R)-(−)-α-thujene, (1S,5S)-(−)-α-pinene, and (1R,2S,6S,7S,8S)-(−)-α-copaene were enantiomerically pure, whereas (R)-(+)-limonene presented a 90.0% enantiomeric excess. All the other analysed chiral compounds were scalemic mixtures. The high distillation yield, its aroma, and the bibliographic bioactivity profile make this essential oil potentially interesting from a commercial point of view. To the best of the authors’ knowledge, this is the first description of an essential oil distilled from leaves of B. sinuata. Full article

The smoke toxicity of epoxy resin limits the application of its carbon fiber composites in marine interior structures. To address this issue, a novel epoxy resin (EZ) was synthesized by grafting phenyl propyl polysiloxane (PPPS) onto ortho-cresol novolac epoxy resin (EOCN), building upon the group’s earlier work on polysiloxane-modified epoxy resin (EB). The results confirmed successful grafting of PPPS onto EOCN, which significantly enhanced the thermal stability and char residue of EZ. Specifically, the peak heat release rate (PHRR), total heat release (THR), peak smoke production rate (PSPR), and total smoke production (TSP) of EZ were reduced by 68.5%, 35%, 73.1%, and 48.3%, respectively, attributable to the formation of a stable and compact char layer that suppressed smoke generation. By blending EZ with EB resin, a low-smoke epoxy system (LJF-2) was developed for prepreg applications. Carbon fiber composites (LJF-CF) prepared from LJF-2 exhibited minimal smoke emission and a unique bilayer char structure: a dense inner layer that hindered smoke transport and a thick outer layer that provided thermal insulation, delaying further resin decomposition. Silicon was uniformly distributed in the char residue as silicon oxides, improving its stability and compactness. Without adding any flame retardants or smoke suppressants, LJF-CF achieved a maximum smoke density (Ds,max) of 276.9, meeting the requirements of the FTP Code for ship deck materials (Ds,max < 400). These findings indicate that LJF-CF holds great promise for use in marine interior components where low smoke toxicity is critical. Full article

To enhance the high-temperature resistance of silicone rubber and meet the application requirements of flexible conductive silicone rubber under elevated temperature conditions, this study adopts a chemical modification strategy by introducing phenyl groups into the molecular chains of silicone rubber to improve its thermal resistance. High-phenyl-content hydroxyl-terminated silicone oil (MPPS) was used as the polymer backbone, and vinylmethyldimethoxysilane (VDMS) served as the chain extender. Through a silanol condensation reaction, vinylmethylphenyl polysiloxane (VMPPS) with a crosslinkable structure was synthesized, providing reactive sites for subsequent vulcanization and molding. Subsequently, needle-like silver-coated glass fiber (AGF) conductive fillers were prepared via a green and environmentally friendly electroless silver plating method. These fillers were incorporated into the phenyl polysiloxane matrix to impart electrical conductivity to the phenyl silicone rubber while synergistically enhancing its thermal resistance. Finally, thermally resistant conductive silicone rubber was fabricated through high-temperature vulcanization, and the key properties of the material were systematically characterized. The synthesized phenyl polysiloxane exhibited a number-averaged molecular weight of up to 181,136, with a PDI of 2.43. When the loading of AGF reached 25 phr, the phenyl silicone rubber composite achieved the electrical percolation threshold, exhibiting a conductivity of 7.12 S/cm. With a further increase in AGF content to 35 phr, the composite demonstrated excellent thermal stability, with a 5% weight loss temperature of 478 °C and a residual mass of 37.36% at 800 °C. Moreover, after thermal aging at 100 °C for 72 h, the conductivity degradation of the phenyl silicone rubber was significantly lower than that of commercial silicone rubber, indicating outstanding electrical stability. This study provides an effective approach for the application of flexible electronic materials under extreme thermal environments. Full article

A significant challenge during the polymer-to-ceramic pyrolysis conversion is to understand the polymer-to-ceramic atomic evolution and correlate the composition changes with the precursor molecular structures, pyrolysis conditions, and resulting ceramic characteristics. In this study, a Reactive Force Field (ReaxFF) simulation approach has been used to simulate silicon oxycarbide (SiOC) ceramic formation from four different polysiloxane precursors. For the first time, we show atomically that pyrolysis time and temperature proportionally impact the new Si-O rich and C rich cluster sizes as well as the composition separation of Si-O from C. Polymer side groups have a more complex effect on the Si-O and C cluster separation and growth, with ethyl group leading to the most Si-O cluster separation and phenyl group leading to the most C cluster separation. We also demonstrate never-before correlations of gas release with polymer molecular structures and functional groups. CH₄, C₂H₆, C₂H₄, and H₂ are preferentially released from the pyrolyzing systems. The sequence is determined by the polymer molecular structures. This work is the first to atomically illustrate the innate correlations between the polymer precursors and pyrolyzed ceramics. Full article

A series of Si-H- or Si-Vi-terminated, branched and linear oligomers containing Me₂SiO segments were prepared by equilibrium polymerization or non-equilibrium polymerization initiated by living anions, respectively. These oligomers were used to improve the defects of concentrated crosslinking points and the high hardness of crosslinked products when using phenyltris(dimethylsiloxy)silane or 1,1,5,5-tetramethyl-3,3-diphenyl trisiloxane as crosslinking agents in the preparation of silicone gel. NMR, FT-IR, and GPC characterized the structure and molecular weight information of the prepared oligomers. The effects of equilibrium polymerization and the anionic non-equilibrium ring-opening polymerization methods on the structure of oligomers were investigated in detail, together with the structure, the molar ratio of SiH to SiVi, and the phenyl content on the thermal properties and the transmittance retention yield of the silicone gel. The introduction of phenyl groups increases the glass transition temperature of silicone gel from −121.29 °C to −117.71 °C when the phenyl content increased from 0.88 wt% to 3.17 wt%. Meanwhile, the thermal decomposition temperature of silicone gel at 10% weight loss in the N₂ atmosphere increased from 440.5 °C to 480.0 °C. When the SiH/SiVi molar ratio is close to 1.0, the transmittance retention yield of the prepared silicone gel using Si-Vi-terminated phenyl T-shaped polysiloxane as the matrix and α, ω-dimethylsiloxyl-terminated PDMS as the crosslinking agent could reach 88.9% after 25 min of UV irradiation. Full article

The Silres H62C methyl-phenyl-vinyl-hydrogen polysiloxane is a promising candidate as a SiC precursor for 3D printing based on photopolymerization reaction. An in-depth nuclear magnetic resonance spectroscopy analysis allowed us to determine its structure and quantify its functional groups. The polysiloxane was found to have a highly branched ladder-like structure, with 21.9, 31.4 and 46.7% of mono-, di- and tri-functional silicon atoms. The polysiloxane cross-links from 180 °C using hydrosilylation between silyl groups (8.4% of the total functional groups) and vinyl groups (12.0%) and contains a non-negligible ethoxy content (2.4%), allowing cross-linking through a hydrolyze/condensation mechanism. After converting the polymer into ceramic and thus releasing mainly hydrogen and methane, the ceramic yield was 72.5%. An X-ray diffraction analysis on the cross-linked and pyrolyzed polysiloxane showed that the ceramic is amorphous at temperatures up to 1200 °C and starts to crystallize from 1200 °C, leading into 3C-SiC carbon-rich ceramic at 1700 °C in an argon atmosphere. Full article

Multiblock copolymers containing linear polydimethylsiloxane or polymethyltrifluoropropylsiloxane and ladder-like polyphenylsiloxane were synthesized in a one-step pathway. The functional homopolymer blocks and final multiblock copolymers were characterized using solution and solid-state multinuclear ¹H, ¹³C, ¹⁹F, and ²⁹Si NMR spectroscopy. It was shown that the ladder-like block contains silanol units, which influence the adhesion properties of multiblock copolymers and morphology of their casted films. The adhesion to metals and mechanical properties of multiblock copolymers were tested. The SEM study of casted films of multiblock copolymers shows the variety of formed morphologies, including long-strip-like or globular. Full article

In this study, a fast curable polysiloxane-silphenylene hybrimer (PSH) was synthesized by the nonhydrolytic sol–gel condensation of phenyl-vinyl-oligosiloxane (PVO) and tris(dimethylhydrosilyl)benzene (TDMSB) under a Pt catalyst to investigate its optical property and thermal stability. The combination of PVO and tripod-type TDMSB results in a hybrimer with a fast curing time of 30 min. The PSH exhibited a high refractive index of 1.60, 1.59, and 1.58 at 450, 520, and 635 nm, respectively. High transmittance of 97% at 450 nm was obtained. The PSH exhibited a very high transmittance of 97% before thermal aging. The high optical transmittance of the PSH was only slightly decreased by 0.5% of the transmittance at 180 °C for 72 h after thermal aging, and high transparency was maintained almost constant even after 72 h of high-temperature treatment. Full article

The excellent performance and wide applications of phenyl polysiloxanes are largely due to their phenyl units and monomer sequences. However, the relationship between molecular structure and material properties has not been explicitly elucidated. In this work, the sequence distribution and microstructure of random copolymers were quantitatively investigated by means of a molecular dynamics (MD) simulation combined with experimental verification. The results of ²⁹Si NMR showed that the large number of phenyl units not only shortened the length of the dimethyl units, but also significantly increased the proportion of consecutive phenyl units. The simulation results indicated the attraction between adjacent phenyl groups that were effectively strengthened intra- and inter- molecular interactions, which determined the equilibrium population of conformations and the dynamics of conformational transitions. Furthermore, the evolution of bond angle distribution, torsion distribution, and mean-squared displacements (MSD) shed light on the conformational characteristics that induce the unique thermodynamics properties and photophysical behavior of high-phenyl polysiloxanes. Differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), spectrofluorimetry, and laser scanning confocal microscopy (LSCM) were performed to verify the conclusions drawn from the simulation. Overall, the complementary use of MD simulations and experiments provided a deep molecular insight into structure–property relationships, which will provide theoretical guidance for the rational design and preparation of high-performance siloxanes. Full article

In this work, a thermal degradation mechanism of room temperature vulcanized (RTV) phenyl silicone rubber that was vulcanized by different crosslinking agents was discussed. Firstly, RTV phenyl silicone rubber samples were prepared by curing hydroxyl-terminated polymethyldiphenylsiloxane via three crosslinking agents, namely, tetraethoxysilane (TEOS), tetrapropoxysilane (TPOS), and polysilazane. Secondly, the ablation properties of RTV phenyl silicone rubber were studied by the muffle roaster test and FT-IR. Thirdly, thermal stability of the three samples was studied by thermogravimetric (TG) analysis. Finally, to explore the thermal degradation mechanism, the RTV phenyl silicone rubber vulcanized by different crosslinking agents were characterized by TG analysis-mass spectrum (TG-MS) and pyrolysis gas chromatogram-mass spectrum (pyGC-MS). Results showed that the thermal stability of RTV phenyl silicone rubber is related to the amount of residual Si–OH groups. The residual Si–OH groups initiated the polysiloxane chain degradation via an ‘unzipping’ mechanism. Full article

A new type of polysiloxane copolymers, with conjugated–regioregular poly(3-hexylthiophene) (P3HT) and non-conjugated-poly(ethylene glycol) (PEG)-grafts have been synthesised, and their properties have been studied alongside those of the parent conjugated polymer (P3HT). Spectroelectrochemical and conductometric analyses revealed an early rise of the conductance of the polymers. Once spectral changes begin taking place, the conductance is stable, implying a loss of mobility of charge carriers, even though standard doping/dedoping patterns are observed. Prototype bulk heterojunction solar cells have been fabricated, based on P3HT/[6,6]-Phenyl-C61-butyric acid methyl ester (PCBM), as well as by substituting P3HT for each of the copolymers. The prototype solar cells achieved PCEs of up to 2.11%. This is one of the highest reported power conversion efficiency (PCE) for devices based on P3HT with low average molecular weight M_n = 12 kDa. Strong correlation between the structure of the copolymer and its photovoltaic performance was found. Elongation of PEG copolymer chain and the use of methyl group instead of terminal hydroxyl groups significantly improved photovoltaic performance. Full article

Two different gas chromatography coupled to quadrupole-time of flight mass spectrometry (GC-QTOF-MS) methodologies were carried out for the analysis of phytosterols and tocopherols in the flesh of three mango cultivars and their by-products (pulp, peel, and seed). To that end, a non-polar column ((5%-phenyl)-methylpolysiloxane (HP-5ms)) and a mid-polar column (crossbond trifluoropropylmethyl polysiloxane (RTX-200MS)) were used. The analysis time for RTX-200MS was much lower than the one obtained with HP-5ms. Furthermore, the optimized method for the RTX-200MS column had a higher sensibility and precision of peak area than the HP-5ms methodology. However, RTX-200MS produced an overlapping between β-sitosterol and Δ⁵-avenasterol. Four phytosterols and two tocopherols were identified in mango samples. As far as we are concerned, this is the first time that phytosterols have been studied in mango peel and that Δ⁵-avenasterol has been reported in mango pulp. α- and γ-tocopherol were determined in peel, and α-tocopherol was the major tocopherol in this fraction (up to 81.2%); however, only α-tocopherol was determined in the pulp and seed. The peel was the fraction with the highest total concentration of phytosterols followed by seed and pulp, and “Sensación” was the cultivar with the highest concentration of total phytosterols in most cases. There were no significant differences between quantification of tocopherols with both columns. However, in most cases, quantification of phytosterols was higher with RTX-200MS than with HP-5ms column. Full article