• Bulletin of the Korean Chemical Society
• /
• v.31 no.3
• /
• pp.582-587
• /
• 2010

A rhodium-catalyzed reductive cleavage reaction of carbon-cyano bonds is developed using hydrosilane as a mild reducing agent. A wide range of nitriles, including aryl, benzyl, and $\beta$-hydrogen containing alkyl cyanides are applicable to this decyanation reaction. The method is also applicable to organic synthesis, in which benzyl cyanide is used as a benzyl anion equivalent and a cyano group functions as a removable ortho-directing group.

• Journal of Integrative Natural Science
• /
• v.2 no.1
• /
• pp.1-12
• /
• 2009

This miniaccount presents the selective examples of our recent discoveries in the photopolymerization of vinyl monomers using the organic initiators such as hydrosilanes, poly(hydroarylsilane)s, benzoin silyl ethers, and thianthrene cation radical. In the photopolymerization of vinyl monomers with silanes polysilanes, while the polymerization yields and polymer molecular weights of the poly(MMA)s containing the silyl moieties decreased, the TGA residue yields and intensities of SiH stretching IR bands increased as the mole ratio of the silanes over MMA increased. The hydroarylsilane and poly(hydroarylsilane) seemed to influence strongly on the photopolymerizaiton of olefinic monomers as both chain initiation and chain transfer agents. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. Benzoin silyl ethers and thianthrene cation radical also exhibit the photoinitiating ability in the photopolymerization of MMA.

• Journal of Korean Ophthalmic Optics Society
• /
• v.5 no.2
• /
• pp.87-90
• /
• 2000

Poly(HEMA)s have been used as the optometric material for the preparation of soft contact lens. The bulk thermal polymerization of 2-hydroxyethyl methacrylate (HEMA) with various hydrosilanes such as $phSiH_3$, $phMeSiH_2$, and $ph2SiH_2$ were performed to produce poly(HEMA)s containing phenylsilyl end moeity. It was found for thermal polymerization that while the polymerization yield and polymer molcular weights decreased as the relative phenylsilane concentration increases, the TGA residue yields and the relative intensities of SiH IR stretching bands increased as the relative hydrosilane concentration increases over HEMA. The polymerization yield, molecular weight, and TGA residue for the thermal polymerization were higher than those for the photo polymerization. Thus, the hydrosilanes significantly influence on the polymerization as both chain-initiation and chain-transfer agents.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.10
• /
• pp.1661-1664
• /
• 2007

Direct reaction of elemental silicon with a gaseous mixture of isopropyl chloride (1) and hydrogen chloride in the presence of copper catalyst using a stirred bed reactor equipped with a spiral band agitator gave isopropyldichlorosilane having a Si-H bond (2a) as a major product and isopropyltrichlorosilane (2b) along with chlorosilanes, trichlorosilane and tetrachlorosilane. A process for production of 2a was maximized using the 1:0.5 mole ratio of 1 to HCl and smaller size of elemental silicon at a reaction temperature of 220 °C. When a reaction was carried out by feeding a gaseous mixture of 1 [12.9 g/h (0.164 mol/h)] and HCl [2.98 g/h (0.082 mol/h)] to a contact mixture of elemental silicon (360 g) and copper (40 g) under the optimum condition for 45 h, 2a among volatile products kept up about 82 mol % until 35 h and then slowly decreased down 68 mol % in 45 h reaction. Finally 2a was obtained in 38% isolated yield (based on 1 used) with an 85% consumption of elemental silicon in a 45 h reaction. In addition to 2a, 2b was obtained as minor product along with chlorosilanes, trichlorosilane, and tetrachlorosilane. The decomposition of 1 was suppressed and the production of 2a improved by adding HCl to 1.

• Journal of Korean Ophthalmic Optics Society
• /
• v.8 no.2
• /
• pp.129-134
• /
• 2003

A wide variety of unsaturated vinyl derivatives can be induced to undergo free-radical chain polymerization. The capability to carry out a thermodynamically feasible polymerization relies on its kinetic feasibility on whether the proceeds at a reasonable rate under a given set of reaction conditions. Initiator or promoter is often required to achieve the kinetic feasibility. Only a few unsaturated monomers including methyl methacrylate(MMA) are known to absorb light between 250 and 500 nm which is the most convenient wavelength range. Also, the polysilanes with unusual optical and electronic properties have been used as ceramic precursors, deep UV photoresists, photoconductors. The hydrosilation has been used to make many interesting types of silicon containing polymers such as copolymer, dendrimers. Bulk polymerization of monomers with different molar radio of hydrosilanes(9:1 through 1:9) were performed. A quartz test tube charged with monomer and hydrosilane was degassed and irradiated with 250 nm UV for 6 hours. The polymer was taken in toluene, precipitated in hexane, filtered off, and dried. It was found that the initiators appeared to competitively and concurrently function as both chain initiation and transfer agents in the polymerization of vinyl monomers.

• Journal of Integrative Natural Science
• /
• v.2 no.1
• /
• pp.18-23
• /
• 2009

This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.