• Fibers and Polymers
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• 제5권4호
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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.

• 통합자연과학논문집
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• 제2권1호
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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.

• 폴리머
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• 제30권6호
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• pp.519-524
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• 2006

나노피막을 형성하는 유기솔더 보존제의 주성분인 저분자 imidazole계 유기물을 대체할 수 있는 고분자 물질을 합성하였다. Cu와 같은 금속과의 접착성이 종은 비닐 피리딘을 주요 단량체로 하였고 물성 개질을 위한 공중합용 단량체로 아크릴아미드와 알릴아민을 사용하였다. 다양한 조성의 공중합체를 제조하여 코팅성, 용해도, 열적 특성, 산화방지 특성 등의 유기솔더 보존제로서의 특성을 평가하였다. 공중합체중 알릴아민을 함유한 공중합체의 경우 전반적으로 Cu pad에 대해 뛰어난 코팅능과 열적안정성을 보였고, 분자량 및 알릴아민 함유량에 따라 그 특성이 변화하였다. Oxygen induced temperature를 측정하여 시간에 따른 열 안정성을 확인해 본 결과 $230^{\circ}C$까지는 70분이상 동안 아무런 산화반응에 의한 열량 변화를 관찰할 수 없었고, 모든 알릴아민계 공증합체가 산소조건하에서 $200^{\circ}C$에서 1시간 동안 무게감량의 변화가 거의 없었으므로 충분한 열적 안정성을 갖고 있는 것으로 확인되었다.