• Journal of Integrative Natural Science
• /
• v.3 no.2
• /
• pp.61-71
• /
• 2010

Hydrosilanes possessing reactive Si-H bond are used in synthesizing various types of polysilanes by dehydrocoupling under the influence of various organometallic promoters. Catalytic Si-Si/Si-O coupling of hydrosilanes with hydrosilanes, alcohols, and lactones to silicon-based polymers are described in this article as selective examples of our recent research developments. These silicon-containing polymers can be used as a precursor to prepare useful functional materials for fabricating electronic devices.

• Bulletin of the Korean Chemical Society
• /
• v.22 no.12
• /
• pp.1337-1340
• /
• 2001

The bulk photopolymerization of methyl methacrylate (MMA) with para-substituted phenylsilanes such as F-C6H4SiH3 (1), H3C-C6H4SiH3 (2), and H3CO-C6H4SiH3 (3) was performed to produce poly(MMA)s containing the respective silyl moiety as an end group. For all the hydrosilanes, the polymerization yields and the polymer molecular weights decreased, whereas the TGA residue yields and the relative intensities of Si-H IR stretching bands increased as the relative silane concentration over MMA increased. The polymerization yields and polymer molecular weights of MMA with 1-3 increased in the order of 3 < 1 < 2. These hydrosilanes influence significantly upon the photopolymerization of MMA as both chain-initiation and chain-transfer agents.

• 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.

• 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.18 no.2
• /
• pp.164-170
• /
• 1997

Via hydrosilation-alkenylation approach using hydrosilanes (HSiMeCl2 and HSiCl3) and allylmagnesium bromide with siloxane tetramer (MeCH2=CHSiO)4 as core molecule, noble carbosilane dendrimers with 12, 24, 48 and 96 allylic end groups have been prepared. The reaction path of the repetitive alkenylation and hydrosilation was monitored by means of NMR spectroscopic measurements. Every step for the formation of dendrimer provided almost quantitative yields as pure dendrimers. Based on the observation of UV spectroscopic measurements of Gn (n=1-4) molecules containing allylic end groups, the maximal molal absorption coefficients (εmax) at λmax and the number of double bonds proved an exponentially increased correlation.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.12
• /
• pp.1103-1107
• /
• 1994

Interaction of triethylsilane and diphenylsilane ($Ph_2$$SiH_2$, $Ph_2$$SiD_2$) with the surfaces of rhodium has been examined by trapping the reaction intermediates with 2,3-dimethyl-l,3-butadiene. 1,4-Hydrosilylation of the diene is predominantly observed to occur under mild condition over the rhodium catalyst. It is inferred from the product analyses that silylene and silyl radicals bonded to rhodium surfaces are the intermediates for addition of silylene to the diene, and for 1,4-hydrosilylation, respectively.

• Journal of Integrative Natural Science
• /
• v.2 no.4
• /
• pp.289-292
• /
• 2009

Perchlorosilanes are useful precursors for the synthesis of hydrosilanes for the fabrication of electronic devices such as silicon thin-film transistors and silicon nanoparticles. For this solution process, requirements of precursors applicable to solution process are relatively low volatile and soluble in common organic solvents. In this work, the decaphenylcyclopentasilane has been obtained from the reaction of the lithium wire and dichlorodiphenylsilane. The reaction of decaphenylcyclopentasilane with lewis acid catalyst, HCl/$AlCl_3$, gives the perchlorocyclopentasilane. Decaphenylcyclopentasilane exhibits an unusual optical property. Its optical property was characterized by UV-vis and fluorescence spectroscopy. Absorption wavelength maxima for the decaphenylcyclopentasilane was 272 nm. Decaphenylcyclopentasilane displayed an emission band at 741 nm with excitation wavelength of 272 nm.

• 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.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.