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4,4-비스[(트리플로로아세톡시)메틸]-1,6-헵타디인의 고리화중합을 통한 공액구조 고분자의 합성
제갈영순,임권택,진성호 한국화상학회 2019 한국화상학회지 Vol.25 No.1
전이금속촉매를 사용한 4,4-비스[(트리플로로아세톡시)메틸]-1,6-헵타디인의 고리화중합을 통하여 고분자 반복단위 내에 고리구조를 갖는 공액구조 고분자인 폴리{4,4-비스[(트리플로로아세톡시)메틸]-1,6-헵타디인}(PBTFMH)을 합성하였다. 일반적으로 몰리브데늄 계 촉매를 사용한 경우의 중합수율이 텅스텐 계 촉매 를 사용한 경우의 그것보다는 높게 나타났다. 합성한 고분자는 중합과정중의 가교화반응으로 대부분 유기 용매에 용해하지 않았다. 고분자의 IR 스펙트럼에서는 단량체의 그것에서 나타났던 아세틸렌의 C≡C, 및 ≡C-H 신축진동띠를 보여주지 않았다. 이 고분자는 XRD 회절분석 결과 대부분 무정형상임이 밝혀졌다. A new conjugated cyclopolymer was synthesized by the cyclopolymerization of 4,4-bis[(trifluoroacetoxy) methyl]-1,6-heptadiyne using various transition metal catalysts. The catalytic avctivity of Mo-based catalysts was found to be more effective than that of W-based catalysts. The resulting polymers were mostly insoluble in organic solvents because of the cross-linking reaction of polymer itself during the polymerization process. The IR spectrum of polymer did not show the acetylenic C≡C and ≡C-H stretching frequencies. And the resulting polymers were found to be mostly amorphorus.
제갈영순,진성호,박종욱,심상연,임권택 한국고분자학회 2021 한국고분자학회 학술대회 연구논문 초록집 Vol.46 No.1
Conjugated polyelectrolytes provide unique properties such as water solubility and processability, variable band gap light absorption and fluorescence, ionic interactions, and aggregation phenomena. Here, we report on the synthesis of a new conjugated polymer with ferrocene moieties by the activated polymerization of 2-ethynylpyridine using (6-bromo-1-oxohexyl) ferrocene. The chemical structure of the resulting conjugated polymer was characterized by IR, NMR, and UV-visible spectroscopies. The electro-optical and electrochemical properties of ferrocene-containing ionic polyacetylene were measured and discussed.
WCl_6-EtAlCl_2 촉매에 의한 폴리(페닐아세틸렌)의 합성과 전자-광 및 전기화학적 특성연구
제갈영순,진성호,장상희,임권택 한국화상학회 2011 한국화상학회지 Vol.17 No.3
WCl_6-EtAlCl_2촉매계를 이용하여 비교적 큰 분자량을 갖는 폴리(페닐아세틸렌)을 합성하였다. 중합반응이 잘 진행되었으며 중합수율은 81%였다. 합성한 폴리(페닐아세틸렌) 분자구조를 NMR (^1H-,^13C-),IR,UV-visible,원소분석 등으로 분석한 결과 페닐 치환기를 갖는 공액구조 고분자가 합성되었음을 확인할 수 있었다. 아울러 332 nm의 빛으로 여기시킬 경우 PL 최대 peak는 424 nm에서 관찰되었는데, 이는 2.93 eV의 광 에너지에 해당한다. 이 고분자의 순환 전압전류 그림은 도핑과 탈도핑사이에서 비가역적인 전기화학적 거동을 보여주었다. 이 고분자의 전기화학적 과정이 매우 안정하였으며, 스캔속도에 따른 산화전류밀도 실험으로부터 이 고분자의 산화-환원 과정은 확산-제어과정에 따르는 것으로 분석되었다. Poly(phenylacetylene) with relatively high molecular weight was prepared by using WCl_6-EtAlCl_2catalystsystem.This polymerization proceeded well in the mild reaction condition to give a high yield of polymer (polymer yield: 81 %). The chemical structure of poly(phenylacetylene) was characterized by such instrumental methods as NMR (^1H-,^13C-),IR,UV-visiblespectroscopies,andelementalanalysistohavetheconjugatedpolymerbackbonebearingphenylsubstituents. The photoluminescence maximum peak of polymer was located at 424 nm, which corresponds to the photon energy of 2.93 eV. The cyclovoltammograms of poly(phenylacetylene) exhibited the electrochemically stable window at the -1.5 ~ +1.5 V region. The kinetics of the redox process of poly(phenylacetylene) was found to be mainly controlled by the reactant diffusion process based on the experiment of the oxidation current density of polymer versus the scan rate.
Cyclopolymerization of 1,1-Dipropargyl-1-silacyclohexane by Transition Metal Catalysts
제갈영순,이인숙,Eun-Hee Chang,Yun-Cheol Jeong,Young-Woo Kwak* 대한화학회 2007 Bulletin of the Korean Chemical Society Vol.28 No.8
A conjugated spirocyclic polymer was synthesized via the cyclopolymerization of 1,1-dipropargyl-1-silacyclohexane with various transition metal catalysts. The monomer, 1,1-dipropargyl-1-silacyclohexane was synthesized by Grignard reaction of 1,1-dichloro-1-silacyclohexane with propargyl magnesium bromide. This polymerization proceeded well to give the corresponding poly(1,1-dipropargyl-1-silacyclohexane). The catalytic activity of WCl6 was found to be similar with that of MoCl5. The structure of polymer having the conjugated backbone with silacyclohexane moieties was characterized by such instrumental methods as NMR (1H-, 13C-), IR, and UV-visible spectroscopies. The resulting polymers were mostly yellow or light-brown powders, depending on the catalyst systems used. This polymer was completely soluble in halogenated and aromatic hydrocarbons such as chloroform, 1,2-dichloromethane, benzene, toluene, and chlorobenzene, etc. The thermal and oxidative stabilities of polymer were also studied and discussed.