• Fibers and Polymers
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• v.5 no.4
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• pp.253-258
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• 2004

Living nature of photoinduced cationic polymerization of isobutyl vinyl ether (IBVE) in the presence of various combinations of diphenyliodonium halide (DPIX), a photocationic initiator and zinc halide $(ZnX_2)$ in methylene chloride has been investigated. Attainment of $100\%$ conversion and a linear relationship between $\%$conversion and number average molar mass of the resulting polymer, strongly suggests the living nature of this system. Livingness of the polymerization system was observed irrespective to the type of halide anion of the initiator and zinc salts unless the reaction temperature is not higher than $-30^{\circ}C$. The rate of polymerization decreases in the order of iodide > bromide > chloride when halide salt of DPIX and $ZnX_2$ are used. It is postulated that the cationic initiation is started by the insertion of weakly basic monomer in to the activated C-X terminal of the monomer adduct which is a reaction product of monomer and HX, a photolytic product of DPIX, formed in situ during the photo-irradiation process. It was concluded that polymerization is initiated by the insertion of weakly basic monomer into activated C- X terminal of monomer adduct due to the pulling action of$ZnX_2$, which successively producing a new polarized C-X terminal for the propagation in cationic nature. This led us to a conclusion that the living nature of this cationic polymerization is ascribable to the polarized C-X growing terminal, which is stable enough to depress the processes of chain transfer or termination process.

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

• Polymer(Korea)
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• v.30 no.6
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• pp.519-524
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• 2006

Poly(4-vinyl pyridine) (PVP) and its copolymers, poly(4-vinyl pvridine- co-acrylamide) and poly(4-vinyl pyridine-co-allylamine), were synthesized and evaluated for application to organic solder-ability preservatives (OSP). The copolymers were synthesized by radical polymerization of vinyl pyridine in the presence of acrylamide or allylamine as a comonomer. Various kinds of polymers with different chemical composition were synthesized by varying the feed ratio of monomers and their low $M_w$ polymers can be obtained by adding 2-mercaptoethanol as a chain transfer agent during poly-merization. All the polymers showed good adhesion properties on Cu pad when they were spin-coated. Especially, allylamine -containing copolymers showed both good adhesion and solubility properties. Also, they exhibited better thermal stability than PVP homopolymer and such thermal properties were changed depending on the chemical composition and their $M_w$, which were evidenced by the measurement of oxygen induced temperature (OIT). From the OIT measurement, poly(4-vinyl pyridine- co-allylamine) was thermally stable up to $230^{\circ}C$ for 70 min in the 100% oxygen environment. As a result, allylamine-containing copolymers can be considered as a promising OSP coating material that has excellent thermal and adhesive properties applicable to the present microelectronic package processes.