本篇論文主要探討單體分子中含有不同可聚合基團化合物的先後聚合,我們以降冰片烯分子連接含有間亞苯二酯基團的分子作為單體,以Grubbs-1催化劑進行開環歧化聚合反應 (ROMP) 得到單股高分子聚合物,以此單股降冰片烯高分子為複製反應的模板,另一端的間亞苯二酯官能基以克萊森酯縮合反應 (Claisen condensation) 進行縮合聚合反應,可以得到不對稱結構的雙股高分子,之後在鹼性條件下水解,得到子鏈高分子寡聚-間亞苯丙酮(Oligo(m-phenylene)acetonylene)。更重要的是,經由GPC的測試結果得知,水解下來的子鏈高分子的分子量可以經由模板來準確的控制,且有良好的分子量分布 (PDI)。此外,我們還研究無模板系統的間苯二乙酯衍生物的縮合聚合反應,其GPC測試結果與模板聚合產物相比,直接縮合聚合後的產物分子量不可控制,且分子量分佈很廣,此控制實驗的結果充分顯示了模板聚合突出的優點:我們能夠經由模板聚合得到分子量分佈窄、且分子量可控制的寡聚-間亞苯丙酮。此寡聚物是一條嶄新的高分子鏈,可供做為石墨烯寡聚物的前驅物。 關鍵字:開環歧化聚合反應;模板聚合;先後聚合;降冰片烯;寡聚-間亞苯丙酮
This thesis describes the sucessesful sequential polymerization of a monomer containing two different polymerizable groups, which can undergo polymerization under different conditions. N-arylpyrrolidine-fused norbornene connected with m-phenylene diacetate moiety is chosen as the starting monomer. This monomer contains norbornene group which can undergo ring-opening metathesis polymerization (ROMP) under various conditions to give well-defined single-stranded polynorbornene skeletons. This polynorbornene backbone can then serve as a template to control Claisen condensation reaction of m-phenylene diacetate moieties to afford the corresponding β-keto ester. This protocols is executed and unsymmetrical ladderphanes are obtained with different degree of polymerization. After hydrolysis under basic conditions, oligo(m-phenylene)acetonylenes with control molecular weight and narrow polydispersity index (PDI) are obtained. It is noteworthy that Claisen condensation of m-phenylene diacetate moiety without templation generated corresponding oligo(m-phenylene)acetonylene with uncontrolled molecular weight and polydispersity index (PDI). Key words: ROMP; Templated polymerization; Sequential polymerization; Norbornene; Oligo(m-phenylene)acetonylene