형광증백제로서 Styrylstilbene 유도체의 합성 및 물성에 관한 연구

Abstract

섬유, 종이 및 펄프 등의 섬유류를 희게 하기 위하여 산화제 또는 환원제를 이용하여 표백을 하는데, 화학 표백된 섬유 및 종이류를 더욱 희게 보이도록 하기 위해 청분처리(bluing) 또는 형광증백처리를 하고 있다. 따라서 형광증백제(flurorescent brightener)는 높은 백도(whiteness)와 견뢰도(fastness)를 가져야 한다. 형광증백제는 반복되는 세탁 등에 따라 씻겨나가는 결과를 초래하여 형광증백처리된 제품에 대한 견뢰도 저하와 환경오염 등에 따른 문제점이 있다. 섬유류의 작용기와 염료의 결합기(linker)를 사용하여 화학반응을 통하여 공유결합을 형성함으로써 염착되는 염료를 반응성 염료라고 한다. 본 연구의 목적은 styrylstilbene계 형광증백제를 반응성 형광증백제로 개발하는 것이다. 4-Amino-4'-nitrostilbene-2,2'-disulfonic acid (1)를 출발물질로 하여 diazotization시킨 뒤 Meerwein arylation를 이용하여 4-nitro-4'-styrylstilbene-2,2'-disulfonic acid (2)를 합성하였다. 4-Amino-4'-styrylstilb- ene-2,2'-disulfonic acid (3)는 iron powder와 acetic acid를 이용한 환원반응으로 합성하였다. Cyanuric acid (4)와 4-(2-hydroxyethylsulfonyl)aniline (5)을 반응 시켜 생성된 중간체인 2-{4-[(4,6-Dichloro-1,3,5-triazin-2-yl)amino]- phenylsulfonyl}ethanol (6) 에 화합물 3의 disodium salt수용액을 첨가하여 두 번째 중간체로 disodium 4-{2-[4-(2-hydroxyethylsulfonyl)- anilino]-4-chloro-1,3,5-triazin-6-yl}amino-4'-styrylstilbene-2,2'-disulfonate (8)을 합성하였다. 중간체 8의 마지막 chloride를 다양한 아민 유도체로 치환시켜 최종 화합물 9a~h를 얻었다. 합성한 화합물의 구조는 ¹H-NMR spectrum과 UV-vis spectrum으로 분석하였다. 또한 다양한 백도를 측정하여 물리적 성질을 확인하였다.; Most of the raw materials were treated with the chemical oxidant to remove their colors. But chemical bleaching method could not completely remove a small quantity of yellowness. Fluorescent brighteners were used as functional pigment in the process of the chemical bleaching to the fiber, paper and pulp in order to make them appear brighter. Fluorescent brighteners should present a high quality of whiteness and fastness. But, the whiteness of the commercial products which were treated with the fluorescent brightener were reduced due to the repeated laundering or external irritant. Reactive dyes are colored compounds that contain one or two groups capable of forming covalent bonds with a given substrate. The purpose of this research is to develop styrylstilbene derivatives as the reactive brighteners. Diazotization of 4-amino-4'-nitrostilbene-2,2'-disulfonic acid and subsequent Meerwine arylation in the presence of copper(Ⅱ) chloride provided 4'-nitro-4-styrylstilbene-2,2'-disulfonic acid (2). The reduction of 4'-nitro group of compound 2 by using the iron power in acidic medium afforded 4'-amino-4-styrylstilene-2,2'-disulfonic acid (3). The addition of the disodium salt solution of compound 3 to the intermediate 6 which were obtained from the reaction of cyanuric acid (4) with 4-(2-hydroxyethylsulfonyl)aniline (5) gave the second intermediate 8, disdium 4-{2-[4-(2-hydroxyethylsulfonyl)anilino]-4-chloro-1,3,5-triazin-6-yl}amino-4'-styrylstilbene-2,2'-disulfonate. Finally, the displacement of the remained chloride in 8 with the various amine derivative provided the target molecules 9a~h. The structure of the synthesized compounds 2, 3 and 9a~h were characterized by the analysis of ¹H-NMR spectrum and confirmed by UV-vis spectrum. The physical properties of compounds 9a~h were performed by whiteness measurement.