To investigate the polymerization systems driven by aromatization energy, 10-methylene-9,10-dihydroanthryl-9-spirocyclopropane (MASC), 10-methylene-9,10-dihydroanthryl-9-spirophenylcyclopropane (MASPC), 8-methylene-1,4-dioxaspiro [4,5] deca-6,9-diene (MDOSD), 8-methylene-1-oxaspiro [4,5] deca-6,9-diene (MOSD) were prepared, and their polymerization behaviors under various conditions and the properties of the resulting polymers were investigated.
Polymerizations of MASC and MASPC were carried out with common radical initiators such as 2,2'-azobisisobutyronitrile, dibenzoyl peroxide. MASPC polymerized well and cleanly in ring-opening fashion accompanied by aromatization. MASC also polymerized well but its polymers were not soluble in solvents probably because of its high crystallinity. All the spectra data indicated that the radical polymerization of MASC and MASPC proceeded with aromatization and ring-opening. Aromatization energy was strong enough driving force to promote 100% ring-opening to insert p-anthrylene groups into the backbone of the resulting polymer. The polymers of MASC and MASPC decomposed above 370℃ as determined by TGA. The electrical conductivity of the polymer even in the doped state failed to show high conductivity (10$^{-7}$-10$^{-8}$S/cm, but deserves further work.
MDOSD polymerized well with various cationic initiators and cleanly in ring-opening accompanied by aromatization. This behavior was confirmed by model study employing $^1H-NMR$, $^{13}C-NMR$, IR spectra of monomers and polymers. The polymer of MDOSD had a glass transition at 15℃ detected by DSC and decomposed above 456℃ as shown on TGA.
Radical polymerization of MDOSD with AIBN took place in high conversion and the main structure was similar to that of cationic polymerization except the rise of small side peaks in the NMR spectra. This system is a rare instance in that alkoxy radical generated by ring-opening driven by aromatization energy was propagating species and polymerization took place in 1,9-type ring-opening polymerization.
MOSD was synthesized and subjected to polymerization, but it was less reactive than MDOSD. The polymerization yield was small and the molecular weight of the obtained polymer was lower than that in the case of MDOSD. However, all the spectral data of the polymers indicated that both cationic and radical polymerization took place cleanly in ring-opening fashion driven by aromatization energy.
방향족화 에너지에 의한 중합계를 연구하기 위하여 10-메틸렌-9,10-디히드로안스릴-9-스피로시클로프로판 (MASC), 10-메틸렌-9,10-디히드로안스릴-9-스피로페닐시클로프로판 (MASPC), 8-메틸렌-1,4-디옥사스피로[4,5]데카-6,9-디엔 (MDOSD), 8-메틸렌-1-옥사스피로[4,5]데카-6,9-디엔 (MOSD)을 합성하고, 다양한 조건에서 중합거동과 중합된 고분자의 특성을 연구하였다. MASPC는 완전하게 방향족화를 경유한 개환 과정을 통해 중합이 잘 진행되었다.
MASC도 역시 중합은 잘 진행되었지만, 고 결정화도에 의한 용매 불용성을 보여주었다. 중합과정중 사용된 방향족화 에너지는 얻어진 고분자 주쇄내에 p-안스릴렌 족을 삽입시키기 위한 100% 개환 과정을 촉진시키는 충분한 추진력이었다. MASC와 MASPC의 고분자는 TGA 측정 결과 약 370℃ 이상에서 분해되었고, 안트라센 부분이 포함되었으나 도핑 된 상태에서도 큰 전도도값을 갖지 못하였다.($10^{-7}\sim10^{-8}$ S/cm)
MDOSD는 다양한 양이온 개시제에 의해 방향족화를 경유하여 완전하게 개환 중합이 진행되었다. MDOSD의 중합체의 유리전이온도는 15℃이고 분해온도는 456℃로 측정되었다. 또한 라디칼 개시제에 의한 MDOSD의 중합은 높은 수율로 얻었으며 주요 구조는 양이온 중합체와 비슷하였고 그 중합거동은 1,9 형태의 개환 중합을 보여주었다. 이 계는 방향족화에 의해 유도 되어진 개환 과정의 결과로 생성된 알콕시 라디칼이 연쇄전파종인 희귀한 예이다.
MOSD를 합성하였으며 쉽게 중합이 진행되었지만 MDOSD보다 훨씬 반응성이 낮았다. MDOSD와 비교하면 중합수율도 낮고 얻어진 중합체의 분자량도 훨씬 작았다. 그러나 스펙트럼 자료에 의하면 양이온과 라디칼개시제에 의하여 완전히 방향족화 에너지에 의해 개환 되었음을 보여 주었다.
