학술논문
주 사슬에 셀레나졸을 포함하는 새로운 단량체의 합성 및 이를 이용한 공액 전도성 고분자의 중합과 이온성 액체와의 상호작용 연구 / Synthesis, Characterization and Properties of New Conjugated Polymers with New Aromatic Selenazole Cyclic Ring in The Main Chain
Document Type
Dissertation/ Thesis
Author
Source
Subject
Language
Korean
Abstract
본 연구는 칼코겐족 원자를 응용한 단량체들의 성질을 탐구하고자 셀레늄이 들어간 물질을 타겟으로 선정하여 합성하고 유사 헤테로 사이클과 비교분석 하였다. 셀레나졸을 기반으로 하는 신규 물질을 2-heptadecylthieno[3,4-d]thiazole (HTS)의 물질을 9단계를 거쳐 합성하였다. 그 후 유사 헤테로 고리화 화합물 두 가지를 합성하였다. 그 후, 유사 물질인 2-heptadecyl-4,6-dihydro-th ieno[3,4-d]thiazole (HTT)와 2-heptadecyl-4,6-dihydroselenopheno[3,4-d]th iazole (HST)를 합성하고 각각 분광학적 분석 비교, 열적 안정성 비교, 전기화학적 비교 연구를 진행하였다. 본 연구에서는, 향후 고분자 태양전지에서 빛을 흡수하는 donor로 사용하기 위해 낮은 밴드 갭을 가지면서, 근적외선 영역까지의 넓은 흡수 범위를 보이는 4가지 고분자를 합성하였다. 4,6-dibromo-2-heptadecylthieno[3,4-d][1,3]selenazole (HTS) (8)를 응용하여 먼저 동중합체인 poly(2-heptadecylt hieno[3,4-d][1,3]selenazole) (PHTS) (9)를 합성하였다. 공액 길이 증대를 위하여 바이닐기를 도입하여 poly(2-heptadecyl-4-vinylthieno[3,4-d][1,3]sel enazole) (PHVTS) (10)를 합성하였다. 향후 고분자 태양 전지에 응용하기 위해서 전자 주개-받게 고분자를 중합했다. 따라서 먼저 단량체를 전자 주개로서 응용하여 전자 받개 그룹인 DPP와 함께 poly(3-(5-(2-heptadecylthi eno[3,4-d][1,3]selenazol-4-yl)thiophen-2-yl)-2,5-bis(2-hexyldecyl)-6-(thio phen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) (PHSTDPP) (11)라는 공중합체를 합성하였다. 다음은 단량체를 전자 받개로 이용하여 전자 주개 그룹인 BDT와 poly(4-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2-yl)-2-heptadecylthieno[3,4-d][1,3]selenazole) (PBDTH TS) (12) 공중합체를 만들었다. 합성한 고분자의 광학적, 물리적, 전기화학적 성질을 측정하였다. GPC (gel permeation chromatograpy), TGA (ther mogravimetric analysis), UV-Vis spectroscopy, CV (cyclic voltametry), c onductivity 등을 이용하여 고분자 성질 측정을 하였다. 본 연구에서는 PHVTS와 이온성 액체와의 상호작용을 연구하여 PHVT S 자체의 광학적, 물리적, 전기화학적 성질을 향상시키는 것을 목표로 하였다. 본 연구진은 UV-Vis spectrophotometer, confocal raman spectroscopy, FT-IR (fourier-transform infrared spectroscopy), AFM (atomic force mic roscopy), 전도도를 측정하여 PHVTS와 이온성 액체의 상호작용을 확인하였다. 표면의 변화와 거칠기를 확인하기 위해서 AFM을 측정하였다. 이미다졸륨 그룹을 갖고 있는 비양성자성 이온성 액체인 [EMIM]Br, [BMIM]Br, 암모늄 그룹을 갖고 있는 양성자성 이온성 액체인 TEMS 각각을 합성한 전도성 고분자인 이온성 액체 혼합물을 제조하였다. 이렇게 만든 전도성 고분자와 이온성 액체의 혼합물을 가지고 광학적, 물리적, 전기화학적 특성들을 확인하였다.
In this study, selenium containing materials were synthesized and cara cterized to investigate the properties of monomer using chalcogen group s. A novel substance based on selenazole was synthesized through 9 steps of 2-heptadecylthieno [3,4-d]thiazole (HTS). 2 similar heterocyclic thi azole compounds were then synthesized. Then, 2-heptadecyl-4,6-dihydrothieno[3,4-d]thiazole (HTT) and 2-heptadecyl-4,6-dihydroselenopheno[3,4-d]thiazole (HST) and analyzed optical analysis, thermal stability, and performed electrochemical studies. In this study, we synthesized 4 polymers with low band gap and wide absorption range up to the near infrared region for use as a donor to absorb light in polymer solar cell. Poly(2-heptadecylthieno[3,4-d][1,3]selenazole) (PHTS) (9) were synthes ized. Poly(2-heptadecyl-4-vinylthieno[3,4-d][1,3]selenazole) (PHVTS) (10) was synthesized by introducing a vinyl group to increase the conjuga tion length. In order to apply synthesized polyemrs to polymer solar cell s in the future, an electron donor-acceptor polymer was prepared. The HTS was used as an electron-donor to synthesize a copolymer called P oly(3-(5-(2-heptadecylthieno[3,4-d][1,3]selenazol-4-yl)thiophen-2-yl)-2,5-bis(2-hexyldecyl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dion e) (PHSTDPP) (11) together with electron donor group DPP. Next, usin g the monomer as an electron acceptor, the electron donating group BD T and Poly(4-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2-yl)-2-heptadecylthieno[3,4-d][1,3]selenazole) (PBDTHTS) (1 2). The optical, physical, and electrochemical properties of the synthesize d polymer were identified. To improve the optical, physical and electrochemical properties of PHVTS through interaction between PHVTS and ionic liquid. We performed further characterization by using UV-Vis spectrophotometer, confocal raman spectroscopy, FT-IR (fourier-transform infrared spectroscopy), AFM (atomic force microscopy) and conductivity. [EMIM]Br and [BMIM]Br, which are aprotic ionic liquids having an imidazolium group, and TEMS, which is a protic ionic liquid having an ammonium group, was prepared as a conductive polymer. The optical, physical, and electrochemical properties of the conductive polymer and the ionic liquid were confirmed.
In this study, selenium containing materials were synthesized and cara cterized to investigate the properties of monomer using chalcogen group s. A novel substance based on selenazole was synthesized through 9 steps of 2-heptadecylthieno [3,4-d]thiazole (HTS). 2 similar heterocyclic thi azole compounds were then synthesized. Then, 2-heptadecyl-4,6-dihydrothieno[3,4-d]thiazole (HTT) and 2-heptadecyl-4,6-dihydroselenopheno[3,4-d]thiazole (HST) and analyzed optical analysis, thermal stability, and performed electrochemical studies. In this study, we synthesized 4 polymers with low band gap and wide absorption range up to the near infrared region for use as a donor to absorb light in polymer solar cell. Poly(2-heptadecylthieno[3,4-d][1,3]selenazole) (PHTS) (9) were synthes ized. Poly(2-heptadecyl-4-vinylthieno[3,4-d][1,3]selenazole) (PHVTS) (10) was synthesized by introducing a vinyl group to increase the conjuga tion length. In order to apply synthesized polyemrs to polymer solar cell s in the future, an electron donor-acceptor polymer was prepared. The HTS was used as an electron-donor to synthesize a copolymer called P oly(3-(5-(2-heptadecylthieno[3,4-d][1,3]selenazol-4-yl)thiophen-2-yl)-2,5-bis(2-hexyldecyl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dion e) (PHSTDPP) (11) together with electron donor group DPP. Next, usin g the monomer as an electron acceptor, the electron donating group BD T and Poly(4-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2-yl)-2-heptadecylthieno[3,4-d][1,3]selenazole) (PBDTHTS) (1 2). The optical, physical, and electrochemical properties of the synthesize d polymer were identified. To improve the optical, physical and electrochemical properties of PHVTS through interaction between PHVTS and ionic liquid. We performed further characterization by using UV-Vis spectrophotometer, confocal raman spectroscopy, FT-IR (fourier-transform infrared spectroscopy), AFM (atomic force microscopy) and conductivity. [EMIM]Br and [BMIM]Br, which are aprotic ionic liquids having an imidazolium group, and TEMS, which is a protic ionic liquid having an ammonium group, was prepared as a conductive polymer. The optical, physical, and electrochemical properties of the conductive polymer and the ionic liquid were confirmed.