PART I. Syntheses and Properties of Polyureas 2,5-Thiophenylene inkage.
ThDI was prepared by unusual reaction of adipic acid with thionyl chloride and pyridine followed by nucleophilic reaction and Curtius rearrangement.
Polyureas containing 2,5-thiophenylene linkage were obtained by the solution polycondensation of ThDI with various diamines in DMF at room temperature.
ThDI and the resulting polyureas are characterized by spectroscopic methods. The resulting polyureas had inherent viscosities in the region of 0.43-0.68 dL/g. Most of these polyureas were soluble in polar solvents, but polyurea prepared from p-phenylenediamine was quite insoluble in organic solvents.
The thermal properties of polyureas were investigated. Polyureas synthesized from aromatic diamines revealed better thermal stability than aliphatic ones. It was found that the polyureas were decomposed before reaching the melting temperature.
Part II. Synthesis and Properties of PolyACAN
Aceanthrylene was prepared by the Friedel-Crafts cyclization of 9-chloroacetyl anthracene followed by reduction with hydride and dehydration.
ACAN was polymerized by radical and cationic initiators, and various transition metal catalysts. It was shown that $TaCl_5$ was the most effective catalyst in the polymerization of aceanthrylene.
The conversions and inherent viscosities of polyaceanthrylene were changed considerably according to the polymerization condition. It was found that maximum conversion and inherent viscosities were 99% and 0.58 dL/g, respectively.
ACAN and the resulting polymer were characterized by spectroscopic methods. It was found that maximum emission and absorption at 430 and 365 nm in ACAN and at 470 and 412 nm in polyACAN, respectively.
The stereoregularity of polyaceanthrylenes prepared in various solvents was determined by $^1H$-NMR and fluorescence spectroscopy. It was found that polyACANs prepared in benzene and chloroform had threo-diisotactic and threo-disyndiotactic structure, respectively.
ACAN was copolymerized with ACN and NVC. According to the nitrogen analyses of the copolymers with NNC, the ratio of NVC in copolymers was slightly higher than those in the feed. The copolymers were also characterized by spectroscopic methods. PolyACAN was soluble in aromatic solvents, tetrahydrofuran, chloroform, and methylenechloride but insoluble in methanol, ethanol, acetone, and pentane.
The thermal properties of polyACAN and copolymers were investigated. Polyaceanthrylene was decomposed at 330℃, and Tm and Tg did not show up.
단원I. 2,5-티오페닐렌 결합을 갖는 폴리우레아의 합성 및 성질
티오페닐렌-2,5-디이소시아네이트는 아디포산과 티오닐클로 라이드와의 반응에서 얻어진 생성물을 친핵치환과 Curtius재배열을 함으로서 합성하였다. 2,5-티오페닐렌 결합을 갖는 폴리우레아는 티오페닐렌-2,5-디이소시아네이트와 여러 디아민을 중합함으로서 합성하였다.
생성된 고분자의 구조는 IR과 $^1H$-NMR 분광법에 의하여 확인되었으며 그 성질도 조사하였다. 고분자의 고유점도는 $0.43 \sim 0.68 dL/g$의 범위에 있었으며 p-페닐렌디아민으로부터 합성된 폴리우레아를 제외한 모든 폴리머들은 극성 유기용매에 잘 녹았다. 방향족 디아민으로부터 만들어진 폴리우레아는 지방족 디아민으로부터 합성된 폴리머보다 상대적으로 좋은 열적 안정성을 보였으나 이 폴리머들은 녹는점에 도달하기 전에 분해하였다.
단원II. 폴리아세안트릴렌의 합성 및 성질
아세안트릴렌은 1-아세안트레논을 환원시켜 얻어진 생성물을 탈수 반응시킴으로서 합성하였다.
아세안트릴렌은 라디칼 및 양이온개시제 또는 여러가지 전이금속 촉매에 의해 중합되었으며 가장 좋은 촉매는 $TaCl_5$로 밝혀졌다. 중합수율과 중합체의 고유점도는 중합조건에 따라 변하였으며 최대수율 및 고유점도는 각각 99%와 0.58 dL/g이였다.
폴리아세안트릴렌의 구조와 입체 규칙성은 분광학적 방법에 의하여 확인하였는데 벤젠 용액과 클로로포름 용액에서 합성된 폴리아세안트릴렌은 각각 트레오-디이소택틱과 신디오택틱 구조를 가지고 있음이 확인되었다. 아세안트릴렌을 아세나프틸렌 및 N-비닐카르바졸과 공중합시킨 결과 그 반응성은 N-비닐카르바졸과 아세나프틸렌의 중간에 위치함을 알았다.
폴리아세안트릴렌은 방향족용매에 잘 녹았으며 알코올이나 아세톤에는 녹지않았다. 폴리아세안트릴렌과 공중합체는 가시광선 영역에서 빛을 흡수하여 액사이머를 형성함으로서 강파장의 빛을 발생하였다. 폴리아세안트릴렌과 공중합체의 열적 성질도 조사하였는데 330℃ 부근에서 해중합과 동시에 분해되었으며 폴리아세나프틸렌과 같이 녹는점이나 글라스전이온도는 보이지 않았다.
