Dimethylsilane Research Articles

A Heteroatom-Containing Functional Poly(Silylenevinylene): Synthesis, Anion Binding, and Sensing of Anion Extraction Processes.

Catalytic hydrosilylation is one of the important synthetic approaches to prepare functional organosilicon polymers. Herein, a functional silicon copolymer is constructed by polyhydrosilylation reaction between a novel 3,7-bis(dimethyl silane)-10-(2-ethylhexyl)-10H-phenothiazine monomer and a neutral tetrapyrrolic macrocycle, namely, 5,5,10,15,15,20-hexamethyl-10α, 20α-bis(4-[ethynylphenyl]) calix[4]pyrrole. The as-constructed copolymer (Mn =9609, PDI=2.2) is investigated as an extractant for organic anions as their tetrabutylammonium salts under interfacial aqueous-organic (water-chloroform) conditions. In this context, a distinctive naked-eye colorimetric as well as fluorescence detection method is developed based on anion-directed hydrogen-bonding interactions. This kind of color/fluorescence monitoring serves as a handy tool for rapid screening of anion extraction processes. The copolymer exhibits high selectivity toward extraction of chloride anion. This study augments the field of polycarbosilanes, poly(silylenevinylene)s in particular, allowing access to a new application window that can be further advanced with good grace in near future.

Thermodynamics of transamination reactions with aminotrimethylsilanes and diaminodimethylsilanes

Abstract Transamination reactions of two different aminosilanes (trimethyl(tert-butylamino)silane and dimethyl(diamino)silane) with amines (diethylamine, pyrrolidine, tert-butylamine, iso-propylamine, and n-propylamine) are studied. For trimethyl(organoamino)silanes, the reaction of trimethyl(iso-propylamino)- or trimethyl(diethylamino)silane as aminosilanes and aniline or pyrrolidine are good starting materials to produce trimethyl(anilino)- and trimethyl(pyrrolidino)silane. The investigated equilibrium constants of the reactions of monoaminosilanes show a good correlation with quantum chemically calculated values. The reaction of two different diaminosilanes Me2Si(NR1R2)2 and Me2Si(NR3R4)2 containing different amino moieties leads to the formation of mixed diaminosilanes Me2Si(NR1R2)(NR3R4) in most cases.

Low energy Si+, SiCH5+, or C+ beam injections to silicon substrates during chemical vapor deposition with dimethylsilane

We found that the atomic-concentration-ratio of carbon to silicon (C/Si ratio) in silicon carbide (SiC) films formed by thermal chemical vapor deposition (CVD) was much greater than 1 when the source gas for CVD was dimethylsilane (DMS). Thus, we tried to change carbon-inclusion levels in the film by injecting some ion beams into a depositing SiC film during the CVD process with DMS. Three ion beams, i.e., Si+, SiCH5+, or C+ ions were injected to depositing SiC films. The energy of Si+, SiCH5+, and C+ ions was 110 eV. The temperature of the substrate was 800 °C. X-ray diffraction of the deposited films showed that 3C–SiC was included in all three samples. X-ray photoelectron spectroscopy (XPS) showed that the C/Si ratio of the obtained SiC film increased significantly following the Si+ or C+ ion beam irradiations. The XPS measurements also showed that the C/Si ratio of the SiC film obtained by injecting SiCH5+ beam during thermal CVD with DMS was lower than that of the SiC film formed by thermal CVD with DMS alone.

Low-energy oxygen ion beam induced chemical vapor deposition using methylsilane or dimethylsilane for the formation of silicon dioxide films

In this study, the ion beam induced chemical vapor deposition method was employed for silicon dioxide (SiO2) film formation using methylsilane (MS) or dimethylsilane (DMS). In a reaction chamber of our ion beam system, O+ ions together with MS or DMS were supplied to a substrate at room temperature. The O+ ion beam had an energy of 100 eV. After the experiment, a film was found to be deposited on the substrate in both MS and DMS cases. The thickness of the resulting film was 60 nm. The results obtained by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) showed that for both MS and DMS, the films were composed of SiO2. In the MS case, XPS data of the film showed that a small amount of carbon was included in the film. On the contrary, in the DMS case, a relatively large amount of carbon was included in the film.

Low-energy Ar+ ion beam induced chemical vapor deposition of silicon carbide films using dimethylsilane

In this paper, a methodology for silicon carbide (SiC) film formation by ion beam induced chemical vapor deposition (IBICVD) using dimethylsilane (DMS) is presented. Both pure DMS gas and Ar+ ion beam were simultaneously injected to a Si substrate. The Ar+ ion energy was 100 eV. The Si substrate temperature was 400, 600, or 800 °C. The duration of each ion beam injection experiment was 10 h. When the substrate temperature was 400 °C, no film formation occurred by the IBICVD experiment. In the case of 600 °C, a film was found to be formed on the substrate by the injection of both DMS gas and Ar+ ion beam. Although Fourier transform infrared (FTIR) spectroscopy measurement of the film showed that the film consisted of SiC, the film thickness was not enough to analyze the film characteristics further. When the Si substrate was set at 800 °C, a film was formed on the substrate by IBICVD. FTIR, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) measurements of the film showed the occurrence of SiC deposition. The XPS measurement also showed that the atomic concentration ratio of carbon to silicon (C/Si ratio) of the film was 1.36. Therefore, excessive C atoms were incorporated to the deposited films. On the contrary, the C/Si ratio of a SiC film prepared by the thermal CVD method using DMS was 1.88. These results suggest that the Ar+ ion beam induced chemical vapor deposition using DMS is useful for reducing of the amount of C atoms to be excessively included in the film.

Analytical pyrolysis of poly(dimethylsiloxane) and poly(oxyethylene) siloxane copolymers. Application to the analysis of sewage sludges

Dimethicone (poly(dimethylsiloxane), PDMS) and its copolymers bearing a poly(ethylene glycol) (PEG) side chain (PEG-12 dimethicone and PEG-8 dimethicone) are utilised as ingredients in personal care products. These materials along with bis-PEG-18 methyl ether dimethyl silane were analysed by Py-GC–MS. The pyrolysates of dimethicone was dominated by cyclic dimethyl siloxanes from D3 to over D10. Besides Dn, the pyrolysates of PEG-dimethicone were featured by the presence of linear dimethyl siloxanes Ln. Hydroxylated siloxanes were also tentatively identified. Pyrograms were also characterised by PEG oligomers with different terminal groups (hydroxyl, ethyl, ethenyl). The molecular structure of pyrolysis products from the combined structural units of PDMS and PEG could not be assigned. Internal standard calibration protocols using pyrolysis products of PEG-12 dimethicone (L6, L8, L9, and triethyleneglycol monoethyl ether) exhibited satisfactory linearity (R2 > 0.992) in the 0.75−58 μg range and repeatability (RSD < 15 %). Three samples of dried sewage sludge from a municipal water treatment plant were extracted with tetrahydrofuran and the extracts analysed by Py-GC–MS. The pyrograms were characterised by intense signals due to the lipid matrix (hydrocarbons, fatty acids, steranes, sterenes, sterols). Dn and Ln were identified indicative for the presence of siloxanes at levels around 60−290 μg gdw−1, while pyrolytic markers of PEG were not revealed. The recovery of PEG-12 dimethicone (17 μg) in spiked sample was 76 %. Galaxolide, galaxolide lactone and triclosan were identified in the pyrograms. The results of this study evidenced the potential of Py-GC–MS as a screening tool for the determination of cosmetic ingredients in sewage sludge.

Production of low-energy SiCH3+ and SiC2H7+ ion beams for 3C-SiC film formation by selecting fragment ions from dimethylsilane

Fragment ions produced from dimethylsilane (DMS) in a Bernas-type ion source were investigated. Dominant fragment ions were identified to be CH3+, Si+, SiH3+, SiCH3+, and SiC2H7+. We mass-selected SiCH3+ and SiC2H7+ ions and then produced low-energy SiCH3+ and SiC2H7+ ion beams. Subsequently, these ion beams were used to irradiate Si(111) substrates at 800 °C. The energies of SiCH3+ and SiC2H7+ ions were set at 100 eV. We found that the irradiation of these ions led to the deposition of silicon carbide (3C-SiC) films on the Si substrates. For comparison, SiC film formations on Si(111) substrates were also attempted by the chemical vapor deposition (CVD) method using DMS. The X-ray photoelectron spectroscopy measurements showed that atomic ratios of C to Si (C/Si ratio) of the films obtained by the irradiation of SiCH3+ and SiC2H7+ ion beams were 1.2 and 1.2, respectively. Conversely, the C/Si ratio of the film obtained by CVD was 1.9. Raman spectroscopy showed that the film obtained by CVD included diamond-like carbon. These results suggest that the low-energy mass-selected ion beam deposition technique using DMS-derived fragment ions is practicable for the 3C-SiC deposition on Si substrates.

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study.

A theoretical analysis of the reaction of oxidative sulfamidation of several alkenes was performed in order to explain the various experimental observations and different reactivity of triflamide and non-fluorinated sulfonamides. Transformations occurring in the system alkene–sulfonamide in the presence of oxidative system (ButOCl + NaI) were analyzed at the MP2/DGDZVP//B3LYP/DGDZVP level of theory using the IEF-PCM method for taking into account the solvent acetonitrile (MeCN) effect. As the model substrates, styrene, trimethyl(vinyl)silane, dimethyl(divinyl)silane and diphenyl(divinyl)silane were chosen and mesylamide, triflamide, tosylamide and p-nosylamide were taken as the reagents. ButOI generated from ButOCl and NaI reacts with sulfonamides to give N-iodinated sulfonamides RSO2NHI and RSO2NI2 as active intermediates, the iodinating activity of the latter being notably higher. The analysis allowed to answer such challenging questions as different reactivity of nonfluorinated sulfonamides leading to aziridination and of triflamide resulting in the formation the main products of bis-triflamidation, or different regioselectivity of halogenation of styrene and trimethyl(vinyl)silane caused by a linear intermediate iodonium cation in the former case and a cyclic one in the latter.

High Thermally Stable and Melt Processable Polyimide Resins Based on Phenylethynyl-Terminated Oligoimides Containing Siloxane Structure.

A series of 4-phenylethnylphthalic anhydride (PEPA)-terminated oligoimides were prepared by co-oligomerizing isomeric dianhydrides, i.e., 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA), 2,3,3′,4′-benzophenonetetracarboxylic dianhydride (a-BTDA) or 2,3,3′,4′-diphenylethertetracarboxylic dianhydride (a-ODPA), with diamines mixture of bis(4-aminophenoxy)dimethyl silane (APDS) and 2,2′-bis(trifluoromethyl) benzidine (TFDB). The effects of siloxane content and dianhydride structure on the rheological properties of these oligoimides and thermal stability of the corresponding cured polyimide resins were investigated. The results indicated that the introduction of the siloxane structure improved the melt processability of the oligoimides, while the thermal stability of the cured polyimide resins reduced. The oligoimide derived from a-ODPA revealed better melt processability and melt stability due to the existence of a flexible dianhydride structure. The oligoimide PIS-O10 derived from a-ODPA gave the lowest minimum melt viscosity of 0.09 Pa·s at 333 °C and showed the excellent melt stability at 260 °C for 2 h with the melt viscosity in the range of 0.69–1.63 Pa·s. It is also noted that the thermal stability of these resins can be further enhanced by postcuring at 400–450 °C, which is attributed to the almost complete chemical crosslinking of the phenyethynyl combined with oxidative crosslinking of siloxane. The PIS-T10 and PIS-O10 resins that were based on a-BTDA and a-ODPA, respectively, even showed a glass transition temperature over 550 °C after postcuring at 450 °C for 1 h.

Synthesis of Novel Carbofunctional Organosilicon Sulfanyl Derivatives of Benzazoles and Triazoles

Previously unknown carbofunctional organosilicon derivatives of azoles are synthesized by the reactions of sulfanyl derivatives of benzoxazole, benzothiazole, benzimidazole, and triazole with (iodomethyl)dimethyl(phenyl)silane and (iodomethyl)(ethynyl)dimethylsilane.

Effect of surfactants on adsorption behavior of nanoparicles at gas-liquid surface

Silica nanoparticles (NPs) are more and more useful in many engineering areas, but the dynamic behaviors of adsorption of NPs at surface are not clear, especially when there exist surfactants on the surface. The modified NPs with the nonionic dimethyl silane are partially hydrophobic, and in this paper, the surface behavior is investigated which is determined by interfacial tension and surface compression modulus. It is concluded that the dimethyl silane coverage, the brine salinity and the surfactant would affect the NPs’ adsorption. Higher salinity in brine or higher dimethyl silane coverage causes lower steady state surface tension, which is related to the hydrophobicity and adsorption amount of NPs at the surface. When the cationic surfactant concentration is lower than critical micelle concentration (CMC), the surface tension of mixture system is a little bit higher than cationic surfactant’s. Cationic surfactant can be adsorbed at NPs’ surface to change the hydrophobicity based on the electrostatic attraction, and then some surfactants are dissolved in liquid phase together with NPs, while the anionic surfactant will not do so. In the shrinking droplet process, the surface tension of the NPs with 1.5 μmol/m&lt;sup&gt;2&lt;/sup&gt; dimethyl silane decreases from ~59 mN/m at the steady state to ~50 mN/m, which proves that the NPs’ adsorption density can be higher even after infinite long time equilibrium due to the repulsive force between the NPs. Besides, the curve of interfacial tension (IFT) versus surface area shows three parts with different declining slopes. In the first part, the relatively low adsorption of NPs at the surface means weak interaction between NPs. Then in the second part, due to the irreversible adsorption, the spacing between NPs decreases with adsorption amount increasing and surface area lowering, so the increasing of NPs’ interaction leads to high surface compression modulus. After that, the IFT curve keeps flat since the NPs assembly reaches to the closest peck. With the increase of NPs’ hydrophobicity, the compression modulus increases up to ~70 mN/m, which satisfies the Gibbs criterion to resist coarsening of the foam or emulsion. However, for the mixing system, increasing surfactant concentration leads to a lower surface tension at steady state, then the surface tension difference or compression modulus decreases too. Finally, we find that the compression modulus order from high to low is as follows: NPs, cationic surfactant-NPs, anionic surfactant-NPs, surfactants. This investigation is meaningful for accounting for the enhancement of foam or emulsion stability with NPs affected by salinity and surfactant.

Formation of Singlet Oxygen during Thermal Degradation of Hydrotrioxides of Triorganosilanes

The yield of singlet oxygen (1O2) due to the degradation of triethylsilane, dimethylphenylsilane, triphenylsilane, and dimethyl(trimethylsiloxy)silane hydrotrioxides has been determined for the first time using the IR chemiluminescence technique. The most effective sources of singlet oxygen in this series are triphenylsilyl hydrotrioxide and dimethyl(trimethylsiloxy)silyl hydrotrioxide. The yield of 1O2 upon their degradation is 69 and 92%, respectively.

Oxidative sulfamidation of vinyl silanes: A route to diverse silylated N-Heterocycles

The reaction of trimethyl(vinyl)silane 1 and dimethyl(divinyl)silane 2 with various sulfonamides in the oxidative system (tert-BuOCl + NaI) has been studied and shown to be an efficient approach for the synthesis of silylated N-heterocycles. Triflamide demonstrated the reactivity principally different from that of arenesulfonamides. With silane 1, it afforded the products of iodochlorination and bis(triflamidation) (major), whereas arenesulfonamides gave N-arenesulfonylaziridines in up to 91% yield. Silane 2 with arenesulfonamides yielded the products of mono and bis(iodochlorination), mono and bis(aziridination), and 3,5-diiodo-4,4-dimethyl-1-(arylsulfonyl)-1,4-azasilinanes. By contrast, triflamide, apart from the products of halogenation and iodotriflamidation, unexpectedly gave 3-(trifluoromethylsulfonyl)-5-(triflamido)oxazolidine as the main product. The structure of most heterocyclic products is proved by X-ray analysis. The effect of the silyl group in the substrate and of the substituent in the reagent on the course of oxidative sulfamidation is discussed by comparing with all-carbon analogues.

Phenylethynyl-terminated oligoimides based on bis(p-aminophenoxy)dimethyl silane: Effect of siloxane structure on processability and thermal stability

A series of phenylethynyl-terminated oligoimides based on 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA), 2,2′-bis(trifluoromethyl)benzidine (TFDB), and bis( p-aminophenoxy)dimethyl silane (APDS) with different siloxane content and various calculated molecular weights were synthesized. The effect of siloxane structure on the processability of oligoimides and the thermal stability of cured polyimides (PIs) was investigated. The results indicated that the oligoimides have lower melt viscosity and broader processing window with the incorporation of flexible siloxane segment. The thermal stability of the cured PIs can be significantly enhanced by high-temperature postcuring due to the oxidative cross-linking of siloxane. The polyimide PI-s1-15 exhibited good balance between processability and thermal stability with the minimum melt viscosity of 0.4 Pa·s at 325°C and glass transition temperature as high as 470°C after postcuring at 450°C. The carbon fiber-reinforced composite T800/PI-s1-15 displayed excellent high-temperature performance, which gave the flexural strength and interlaminar shear strength of 703 and 33 MPa, respectively, when tested at the temperature as high as 450°C.

Silane‐bridged diphosphine ligand for palladium‐catalyzed ethylene oligomerization

In this study, bis(diphenylphosphinemethyl)dimethyl silane (L1) and its palladium(II) halide complex, L1/PdCl2 (C1), were synthesized and characterized. Single‐crystal X‐ray analysis of the complex revealed bidentate coordination at the Pd center. In combination with methylaluminoxane (MAO) as co‐catalyst, C1 exhibited excellent catalytic activity and selectivity for ethylene dimerization toward butene. The maximum catalytic activity obtained from the C1/MAO system for ethylene dimerization to yield butenes was 7.33 × 105 g/(molPd·h). The selectivity toward butene remained stable and high (&gt; 96%) over the various conditions.

Role of free-radical chain reactions and silylene chemistry in using methyl-substituted silane molecules in hot-wire chemical vapor deposition

The reaction chemistry of four methyl-substituted silane molecules, including monomethylsilane (MMS), dimethylsilane (DMS), trimethylsilane (TriMS), and tetramethylsilane (TMS), has been studied in the hot-wire (catalytic) chemical vapor deposition (HWCVD) process, both on heated tungsten or tantalum filaments and in the gas phase. The four molecules dissociate catalytically on hot W or Ta surfaces to form ·CH3, ·H and H2. In a HWCVD reactor setup where the pressure is relatively high at 8–533Pa, two reaction mechanisms involving silylene and free radical intermediate, respectively, operate with the four precursor gases. For MMS, its reaction chemistry is characterized by the exclusive involvement of methylsilylene intermediate. Reaction products when using DMS as a precursor gas come from silylene chemistry and free-radical chain reactions. Filament temperature and pressure affect strongly the competition between the two mechanisms. Specifically, silylene chemistry dominates at low temperatures of 1200–1300°C and a low pressure of 16Pa, and free-radical chain reactions take over at high temperatures and pressures. With the increasing methyl substitutions in TriMS and TMS, free-radical chain reactions become predominant. A clear transition in the operating reaction mechanism from silylene chemistry to free-radical chain reactions has been shown when the number of SiCH3 bonds increases in the methyl-substituted silane molecules.

Silane-bridged diphosphine ligands for nickel-catalyzed ethylene oligomerization

In this study, bis(diphenyl phosphine) dimethyl silane (L1), bis(diphenyl phosphine) methyl dimethyl silane (L2), bis(diphenyl phosphine methyl) dimethyl silane (L3) and their nickel (II) halide complexes, L1/NiBr2 (C1), L2/NiBr2 (C2), L3/NiBr2 (C3), were synthesized and characterized. The X-ray single-crystal analysis of C3 complex showed bidentate coordination on the Ni center. In combination with methylaluminoxane as co-catalyst, these complexes produced catalytic systems for ethylene dimerization to butylene with catalytic activities of up to 3.12 × 106 g mol−1 (cat.) h−1 and selectivities up to 97.6 %. With the fine-tuned ligand backbone, such a PSiP-based catalyst system provides a model for precise understanding of the impact of ligand variations on catalytic performance.

Hydrogen elimination from the dissociation of methyl-substituted silanes on tungsten and tantalum surfaces

The elimination of H2 from the dissociation of four methyl-substituted silane molecules, including monomethylsilane (MMS), dimethylsilane (DMS), trimethylsilane (TriMS), and tetramethylsilane (TMS), on a heated tungsten or tantalum filament surface has been studied using laser ionization mass spectrometry. Two complementary ionization methods, i.e., single photon ionization (SPI) using a vacuum ultraviolet wavelength at 118 nm (10.5 eV) and a dual ionization source incorporating both 10.5 eV SPI and laser-induced electron ionization, were employed to detect the production of H2. Examination of the intensity of the H2+ peak from the four molecules has shown that it increases with temperature until reaching a plateau at around 2000−2100 °C on both tungsten and tantalum filaments. These methyl-substituted silanes are dissociatively adsorbed on tungsten and tantalum surfaces by Si−H bond cleavage, and as the temperature is raised, by C−H bond rupture. Experiments with the isotopomers of MMS, DMS, and TriMS have shown that the formation of H2 follows the Langmuir−Hinshelwood mechanism where two adsorbed hydrogen atoms on metal surfaces recombine to produce H2. The determined activation energy (Ea) for H2 formation from MMS, DMS, and TriMS, in the range of 58.2−93.4 kJ mol−1, has been found to increase with the number of methyl substitutions in the precursor molecule. Comparison of these Ea values with the reported values of 51.1−78.8 kJ mol−1 for the methyl radical formation from the same three precursor molecules has led to the conclusion that the initial Si−H bond cleavage in the dissociative adsorption of MMS, DMS, and TriMS is the rate-limiting step for the formation of both H2 molecules and ·CH3 radicals.

Multi-solution processes of small molecule for flexible white organic light-emitting diodes

Most small molecule organic light emitting diode (SM-OLED) device structures are made in one layer using solution-based processing because the solution is usually a high dissolvent material that easily attacks the layer below it. We demonstrate a simple and reliable stamping technique for fabricating multi-solution process flexible white SM-OLEDs. The structure is anode/spin-hole injection layer/spin-emitting layer/stamping-electron transport layer/cathode. Poly(di-methyl silane) (PDMS) stamp is used for transferring electron transport layer. An intermediate ultraviolet-ozone surface treatment is introduced to temporarily modify the PDMS stamp surface. Then, the solution-based electron transport layer film can therefore be uniformly formed on top of the PDMS surface. After that the electron transport layer film on the PDMS stamp is transfer-printed onto the emitting layer with suitable heating and pressing. A solution-based processing is successfully established to efficiently fabricate flexible white SM-OLEDs. The SM-OLEDs were obtained at the current density of 20mA/cm2, luminance of 1062cd/m2, current efficiency of 5.57cd/A, and Commission internationale de l'éclairage coordinate of (0.32, 0.35).

Synthesis of Bottlebrush Polystyrenes with Uniform, Alternating, and Gradient Distributions of Brushes Via Living Anionic Polymerization and Hydrosilylation

By combining living anionic polymerization and hydrosilylation, densely grafted bottlebrush polymers with controlled spacing of branch points are prepared. Dimethyl(4-vinylphenyl)silane and dimethyl(4-(1-phenylvinyl)phenyl)silane are anionically (co)polymerized to synthesize uniform, alternating, and gradient in-chain silyl-hydride (Si-H) functionalized backbones. The spacing of branch points is controlled effectively by regulating the distribution of Si-H groups along the backbones. Three backbones with a similar number of Si-H groups but variable distributions are used to synthesize corresponding bottlebrush polymers via hydrosilylation between the backbones and chain-end vinyl functionalized polystyrene. The uniformly grafted bottlebrush exhibits the highest hydrodynamic radius (Rh ) of 5.6 nm and the lowest Tg of 79 °C which may be attributed to its compact grafted structure. This methodology exhibits high efficiency and convenience for the construction of bottlebrushes with controlled distribution of brushes.