Vinylsilanes Research Articles

A Characterization Study on Toughening Vinyl Ester Composites Using Annealed Vinyl Silane Functionalized Biosilica from Foxtail Millet Husk and Nettle Fibre

A Characterization Study on Toughening Vinyl Ester Composites Using Annealed Vinyl Silane Functionalized Biosilica from Foxtail Millet Husk and Nettle Fibre

Characterization of vinyl silane–treated areca nut woven fiber and bronze filler toughened polyester composite

Characterization of vinyl silane–treated areca nut woven fiber and bronze filler toughened polyester composite

Probing the Saltwater Immersion Effect on Buried Interfacial Structures between a Sealant and Adhesion Promoter at the Molecular Level.

In this research, we used sum frequency generation vibrational spectroscopy to investigate the buried interface of a thiol-epoxy model aerospace sealant in contact with a silane-based adhesion promoter (6111) following exposures to 3% saltwater at elevated temperatures and elevated temperatures alone. The results suggest that the saltwater caused a change at the interface between the adhesion promoter and sealant, while an elevated temperature of 60 °C itself did not affect the interfacial structure noticeably. Model hydrolyzed and nonhydrolyzed silanes were also used in the study to compare with the adhesion promoter 6111 to understand the interfacial behavior of main silane components in 6111 as well as their potential role in adhesion. The amino silane in 6111 likely segregates more at the sealant/adhesion promoter interface and interacts with the sealant compared to the vinyl silane. The results imply that the saltwater immersion process led to the disordering of the adhesion promoter/sealant interface (caused by interfacial structural randomization), which could potentially have implications for adhesion.

Effects of mechanical and fatigue properties of vinyl silane–treated and ageing-processed areca fibre and bronze nanoparticle–reinforced polyester composite

Effects of mechanical and fatigue properties of vinyl silane–treated and ageing-processed areca fibre and bronze nanoparticle–reinforced polyester composite

Paired Electrolysis Enables Reductive Heck Coupling of Unactivated (Hetero)Aryl Halides and Alkenes.

The formation of carbon-carbon (C-C) bonds is a cornerstone of organic synthesis. Among various methods to construct Csp2-Csp3 bonds, the reductive Heck reaction between (hetero)aryl halides and alkenes stands out due to its potential efficiency and broad substrate availability. However, traditional reductive Heck reactions are limited by the use of precious metal catalysts and/or limited aryl halide and alkene compatibility. Here, we present an electrochemically mediated, metal- and catalyst-free reductive Heck reaction that tolerates both unactivated (hetero)aryl halides and diverse alkenes such as vinyl boronates and silanes. Detailed electrochemical and deuterium-labeling studies support that this transformation likely proceeds through a paired electrolysis pathway, in which acid generated by the oxidation of N,N-diisopropylethylamine (DIPEA) at the anode intercepts an alkyl carbanion formed after radical-polar crossover at the cathode. As such, this approach offers a sustainable method for the construction of Csp2-Csp3 bonds from (hetero)aryl halides and alkenes, paving the way for the development of other electrochemically mediated olefin difunctionalization reactions.

Paired Electrolysis Enables Reductive Heck Coupling of Unactivated (Hetero)Aryl Halides and Alkenes

AbstractThe formation of carbon‐carbon (C−C) bonds is a cornerstone of organic synthesis. Among various methods to construct Csp2−Csp3 bonds, the reductive Heck reaction between (hetero)aryl halides and alkenes stands out due to its potential efficiency and broad substrate availability. However, traditional reductive Heck reactions are limited by the use of precious metal catalysts and/or limited aryl halide and alkene compatibility. Here, we present an electrochemically mediated, metal‐ and catalyst‐free reductive Heck reaction that tolerates both unactivated (hetero)aryl halides and diverse alkenes such as vinyl boronates and silanes. Detailed electrochemical and deuterium‐labeling studies support that this transformation likely proceeds through a paired electrolysis pathway, in which acid generated by the oxidation of N,N‐diisopropylethylamine (DIPEA) at the anode intercepts an alkyl carbanion formed after radical‐polar crossover at the cathode. As such, this approach offers a sustainable method for the construction of Csp2−Csp3 bonds from (hetero)aryl halides and alkenes, paving the way for the development of other electrochemically mediated olefin difunctionalization reactions.

One-Pot Synthesis of Terminal Alkynes from Alkenes.

The direct synthesis of terminal alkynes from widely available terminal alkenes is an unmet challenge in organic synthesis. Here, we show that alkyl and aromatic terminal alkenes can be converted to the corresponding alkynes in a one-pot process consisting of a Ru-catalyzed dehydrogenative hydrosilylation, followed by an oxidative dehydrogenative reaction of the vinyl silane intermediate, enabled by the combination of PhIO with BF3. This formal alkene dehydrogenation reaction with commercially available reagents and under mild reaction conditions gives access to terminal alkynes in a simple manner, including acetylene.

Chemical Modification of Cu2O Nanoparticles with Triacetoxy(Vinyl)Silane: Enhanced Dispersion, Abrasion Resistance, and Thermal Stability in Acrylic Coatings

Chemical Modification of Cu2O Nanoparticles with Triacetoxy(Vinyl)Silane: Enhanced Dispersion, Abrasion Resistance, and Thermal Stability in Acrylic Coatings

Effect of vinyl silane–treated plant root waste biomass cellulose on pineapple fiber-vinyl ester composites: a characterization study

Effect of vinyl silane–treated plant root waste biomass cellulose on pineapple fiber-vinyl ester composites: a characterization study

Tris(pentafluorophenyl)borane‐Catalyzed Functionalization of Benzylic C−F Bonds

AbstractThe activation of C(sp3)−F bonds by the commercially available catalyst B(C6F5)3 is reported and applied in reactions with arenes, allylic, vinylic and acetylenic silanes, and olefins to achieve a variety of C−C bond formations (45 examples).

Performance of concrete superficially treated with nano-modified coatings under sulfuric acid exposures

Protection of concrete surface layer is crucial for preserving serviceability and durability of concrete structures during their service life. Chemical attack by sulfuric acid is an aggressive exposure, commonly causing significant damage to concrete elements such as buildings' foundations and basement walls, buildings and structures affected by acid rain, industrial facilities, and wastewater treatment facilities. Hence, this study endeavored to evaluate the performance of nano-modified composites as surface treatments for concrete under severe chemical exposures. Nano-calcium carbonate and nano-clay particles were dispersed at different dosages (0, 2.5, and 5% by mass) in the neat coatings: vinyl ester (membrane-forming polymer) and silane (hydrophobic agent). Moreover, an amorphous colloidal silica (SiO2>50%) was also used as a superficial treatment for concrete. These coatings were applied to concrete specimens with water-to-binder ratios (w/b) of 0.40 (representing good quality/low penetrability concrete treated for prohibition of deterioration) and 0.60 (representing deteriorated/high penetrability concrete in need for rehabilitation). the wettability and initial transport characteristics of the coated concrete specimens were determined. In addition, the durability of superficially treated concrete specimens was examined under two aggressive exposures: full submergence in a 5% (by volume) sulfuric acid solution, and 5% sulfuric acid solution combined with wetting-drying cycles. During both exposures, the deterioration of concrete specimens was observed by visual inspection and quantified in terms of mass change. Furthermore, the damage mechanisms and coatings’ performance were studied by microstructural, mineralogical, and thermal analyses. The overall results showed that vinyl ester and vinyl ester nanocomposites significantly improved the durability of concrete specimens by an average of around 64% relative to that of the silane and silane nanocomposites; hence, they are recommended for field applications.

Fabrication and sensing properties of a molecularly imprinted polymer on a photonic PDMS substrate for the optical detection of C-reactive protein

This work presents the development of a novel photonic-based sensor on a nanoscale patterned polydimethylsiloxane (PDMS) substrate acting as transducer, combined with a molecularly imprinted polymer for the rapid and sensitive detection of C-reactive protein (CRP). A silicon wafer was patterned using electron-beam lithography with a one-dimensional (1D) reflective grating (periodicity of about 400 nm) and then replicated using nanoimprint lithography. The latter silicon mould was used for replica moulding to generate a patterned PDMS. The unique 1D design gave PDMS photonic properties that were suitable as a substrate to assemble the biorecognition layer. The surface of the photonic PDMS was modified to become hydrophilic and additionally functionalized with vinyl silane groups to bind the imprinted polymer, resulting in a photonic molecularly imprinted polymer substrate (PMIPS). The developed method was successfully used to detect CRP in serum samples. The reflectance intensity decreased with increasing CRP concentrations, and the sensing PMIPS showed a linear response between 0.005 and 1.215 µg mL−1, a limit of detection of 0.003 µg mL−1, and a selective response to CRP when tested against serum calprotectin. Overall, this novel optical sensor can be used to detect CRP, a serum biomarker of inflammation, particularly in inflammatory bowel diseases.

Effect of Composite Interface Enhancer on the Cementation Strength of Shale Formation–Cement Ring Interface

The cement strength between the cement and the formation is a key factor in determining the cementation sealing capacity. In the shale formation, due to the organic matter content, the cementing quality between the formation and the cement ring is poor, which affects the quality of cementing. It is easy to cause problems such as annulus pressure. To improve the quality of cementing, this paper investigates the effect of amino silane coupling agents, vinyl silane coupling agents and aluminium–zirconate coupling agents on the interface cementation of rock and cement under different conditions. Meanwhile, the effects of different coupling agent compounding on improving the cementation interface cement strength under different temperature and concentration conditions were investigated. This led to the development of a composite interface enhancer. The composite interface enhancer can improve the bond strength between cement and rock by 189.22%. A preflush fluid system was developed to effectively improve the cementation strength of mud shale formations, and its performance was evaluated. The density of the preflush fluid system is 1.15 g·cm−3, and it has good rheology, settlement stability, and filtration loss. In addition, it improves the cementing interface cementing strength between the cement and shale formation.

Nickel-Catalyzed Reductive Cross-Coupling of Propargylic Acetates with Chloro(vinyl)silanes: Access to Silylallenes.

Because of their various reactivities, propargyl acetates are refined chemical intermediates that are extensively applied in pharmaceutical synthesis. Currently, reactions between propargyl acetates and chlorosilanes may be the most effective method for synthesizing silylallenes. Nevertheless, owing to the adaptability and selectivity of substrates, transition metal catalysis is difficult to achieve. Herein, nickel-catalyzed reductive cross-coupling reactions between propargyl acetates and substituted vinyl chlorosilanes for the synthesis of tetrasubstituted silylallenes are described. Therein, metallic zinc is a crucial reductant that effectively enables two electrophilic reagents to selectively construct C(sp2)-Si bonds. Additionally, a Ni-catalyzed reductive mechanism involving a radical process is proposed on the basis of deuteration-labeled experiments.

Die Totalsynthese von Isoxeniolid A**

AbstractIsoxeniolid A ist ein hochgespanntes marines Diterpenoid aus der Familie der Xenicane. Es steht repräsentativ für eine Unterfamilie von Xenicanen, deren 9‐gliedriger Ring eine allylische Hydroxygruppe aufweist; derartige Xenicane wurden bisher nicht als Zielmoleküle von Totalsynthesen verfolgt. Wir beschreiben hier die erste asymmetrische Totalsynthese eines derartigen Xenicans, nämlich des Isoxeniolid A. Dabei lag der Schlüssel zum Aufbau des besonders herausfordernden E‐konfigurierten Cyclononenrings in einer diastereoselektiven intramolekularen Nozaki–Hiyama—Kishi‐Reaktion. Andere wichtige Transformationen waren eine enzymatische Desymmetrisierung zur Kontrolle der absoluten Stereochemie, eine diastereoselektive Cuprat‐Addition und die Verwendung eines bifunktionalen Vinylsilan‐Bausteins. Unsere Synthesestrategie ermöglicht auch den Zugang zur enantiomeren Form des Naturstoffs sowie prinzipiell zu einer Vielzahl anderer natürlicher Xenicane und synthetischer Analoga für Struktur‐Aktivitäts‐Untersuchungen.

Total Synthesis of Isoxeniolide A.

Isoxeniolide A is a highly strained xenicane diterpenoid of marine origin. This natural product is representative for a subfamily of xenicanes incorporating an allylic hydroxy group in the nine-membered ring; members of this xenicane subfamily so far have not been targeted by total synthesis. Herein, we describe the first asymmetric total synthesis of isoxeniolide A. Key to forming the challenging E-configured cyclononene ring was a diastereoselective intramolecular Nozaki-Hiyama-Kishi reaction. Other important transformations include an enzymatic desymmetrization for absolute stereocontrol, a diastereoselective cuprate addition and the use of a bifunctional vinyl silane building block. Our strategy also permits access to the enantiomer of the natural product and holds potential to access a multitude of xenicane natural products and analogs for structure-activity relationship studies.

Synthesis and characterization of PMMA-grafted-ZrO2 hybrid nanoparticles

In this study, we reported a facile synthesis and the characterization of PMMA-grafted ZrO2 hybrid nanoparticles from original ZrO2 (oZrO2) nanoparticles. The synthesis process included of three steps: (i) modification of nano ZrO2 with a vinyl silane agent, (ii) graft copolymerization of methyl methacrylate (MMA) monomers and modified ZrO2 (mZrO2) nanoparticles, and (iii) extraction of homo PMMA to obtain the final product of PMMA-g-ZrO2 (gZrO2) nanoparticles. Fourier transform infrared (FTIR) spectra and thermogravimetric analysis (TGA) of mZrO2, oZrO2, and gZrO2 indicated that the silane coupling agent was grafted onto oZrO2 nanoparticles. FTIR spectra of gZrO2 indicated PMMA had been successfully grafted onto the surface of ZrO2 nanoparticles. Using TGA method, the PMMA grafting content onto ZrO2 nanoparticles was evaluated as 9.03 wt.%. The electron microscopy (SEM) images of gZrO2, mZrO2, and oZrO2 indicated that their primary particle size and shape were almost unchanged after modification processes, their particle size was in the range from 50 nm to 140 nm. XRD analysis showed the monoclinic crystalline structure of three kinds of ZrO2 nanoparticles (nanocrystals). The organic gZrO2 nanoparticles can be a better candidate as an opacifier additive for polymer nanocomposites or acrylic bone cement.

Preparation and Carbocupration–Silylation of Allyl Propiolates: Vicinal Functionalization To Form Polysubstituted (E)-Vinylic Silanes

AbstractThe preparation and TMSOTf-mediated catalytic carbocupration–silylation of allylic propiolates has been investigated, expanding on previous syntheses of a variety of β-alkyl- and β-aryl-substituted vinylsilanes from an ethyl propiolate precursor. With few exceptions, the series of synthesized O-allyl (E)-vinylsilanes has been isolated in high yields (61–89%) with exceptional diastereoselectivities (E/Z >20:1). Additionally, we demonstrated a novel LDA-initiated, TMSCl-mediated Ireland–Claisen rearrangement of a representative allylic ester.

A Novel Polyester Varnish Nanocomposites for Electrical Machines with Improved Thermal and Dielectric Properties Using Functionalized TiO2 Nanoparticles.

Recently, there has been a growing interest in polymer insulating materials that incorporate nanoscale inorganic additives, as they have shown significantly improved dielectric, thermal, and mechanical properties, making them highly suitable for application in high-voltage insulating materials for electrical machines. This study aims to improve the dielectric and thermal properties of a commercial polyester varnish by incorporating different concentrations of titanium dioxide nanoparticles (TiO2) with proper surface functionalization. Permafil 9637 dipping varnish is the varnish used for this investigation, and vinyl silane is the coupling agent used in the surface functionalization of TiO2 nanoparticles. First, nanoparticles are characterized through Fourier transform infrared spectroscopy to validate the success of their surface functionalization. Then, varnish nanocomposites are characterized through field emission scanning electron microscopy to validate the dispersion and morphology of nanoparticles within the varnish matrix. Following characterization, varnish nanocomposites are evaluated for thermal and dielectric properties. Regarding thermal properties, the thermal conductivity of the prepared nanocomposites is assessed. Regarding dielectric properties, both permittivity and dielectric losses are evaluated over a wide frequency range, starting from 20 Hz up to 2 MHz. Moreover, the AC breakdown voltage is measured for varnish nanocomposites, and the obtained data are incorporated into a finite element method to obtain the dielectric breakdown strength. Finally, the physical mechanisms behind the obtained results are discussed, considering the role of nanoparticle loading and surface functionalization.

Cobalt-Promoted Electroreductive Cross-Coupling of Prop-2-yn-1-yl Acetates with Chloro(vinyl)silanes.

An electroreductive cross-coupling of prop-2-yn-1-yl acetates with chloro(vinyl)silanes for producing tetrasubstituted silylallenes is developed. The method enables the formation of a new C─Si bond through the cathodic reduction formation of the silyl radical, radical addition across the C≡C bond, the alkenyl anion intermediate formation, and deacetoxylation and represents a mild, practical route to the synthesis of silylallenes. Mechanistic studies reveal that CoCl2 acts as the mediator to promote the formation of the alkenyl anion intermediate via electron transfer.