本研究中成功合成出不同構型的含酮基脂環族二酸酐 (1R,2S,3R,4S,4aR,5S,6R,7S,8R,8aR,9aS,10aS)-tetramethyl-4a,8a,9a,10a-tetramethyl-9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (CTMDA)、(1R,2S,3R,4S,4aR,5S,6R,7S,8R,8aS,9aS,10aR)-tetramethyl-4a,8a-dimethyl-9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (CDMDA)與(1R,2S,3R,4S,4aR,5S,6R,7S,8R,8aS,9aS,10aR)-tetramethyl-4a,8a,9a-trimethyl-9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (CTrMDA)。過程中針對合成路徑中的親核取代反應、甲氧基羰基化反應進行探討，除了將實驗流程最佳化以外，也提出了化合物構型轉變的機制，最後藉由X-ray單晶繞射儀表徵其立體構型。三種不同構型含酮基脂環族二酸酐，分別與芳香族二胺4,4’-oxydianiline (ODA)、2,2’-bis(trifluoromethyl)benzidine (TFMB)、4,4'-diamino-2,2'-dimethylbiphenyl (m-Tol)，2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA)、2-trifluoromethyl-4,4'-diaminodiphenyl ether (3FODA)、2,2-bis [4-(4-aminophenoxy)phenyl] propane (BAPP) 進行一步法縮合聚合反應，大部分組合皆展現高分子量，可以形成具有撓曲性的高分子薄膜，並且無色透明。其中CTMDA所合成的聚醯亞胺，在熱性質與加工性方面較為優異，PI-CTrMDA/ODA的玻璃轉移溫度(Tg)達477 ℃，且5 %熱重損失溫度 (Td5%)達481 ℃，並且在室溫下溶於常見的極性非質子溶劑中m-cresol、GBL、NMP、DMAc；CDMDA、CTrMDA所衍生出的聚醯亞胺則是在單體反應性與熱尺寸安定性上較為突出，其分子量 (Mw) 最高可達369 kDa。

In this study, we successfully synthesize three novel ketone-containing alicyclic dianhydrides with different configurations (1R,2S,3R,4S,4aR,5S,6R,7S,8R,8aR,9aS,10aS)-tetramethyl-4a,8a,9a,10a-tetramethyl-9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (CTMDA)、(1R,2S,3R,4S,4aR,5S,6R,7S,8R,8aS,9aS,10aR)-tetramethyl-4a,8a-dimethyl-9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (CDMDA), and (1R,2S,3R,4S,4aR,5S,6R,7S,8R,8aS,9aS,10aR)-tetramethyl-4a,8a,9a-trimethyl-9,10-dioxotetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (CTrMDA)。We optimized the reaction conditions of the nucleophilic substitution reaction and Pd-catalyzed methoxycarbonylation, proposed the mechanism of the configuration change of these compound. Finally, their steric structures were confirmed by X-ray single crystal diffraction. These three different configurations of dianhydrides reacted with 4,4’-oxydianiline (ODA), 2,2’-bis(trifluoromethyl)benzidine (TFMB), 4,4'-diamino-2,2'-dimethylbiphenyl (m-Tol), 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2-trifluoromethyl-4,4'-diaminodiphenyl ether (3FODA), 2,2-bis [4-(4-aminophenoxy)phenyl] propane (BAPP) by one-step polycondensation to form flexible and colorless polyimides with high molecule weights. The polyimide synthesized by CTMDA exhibited excellent thermal properties and processability. The resulting film has a glass transition temperature (Tg) of 477 ℃, and the 5% thermogravimetric loss temperature (Td5%) of 481 ℃, and it is soluble in common polar aprotic solvents, such as m-cresol, GBL, NMP, DMAc; polyimides derived from CDMDA、CTrMDA has excellent monomer reactivity and thermal dimensional stability, and its molecular weight (Mw) can reach up to 369 kDa.

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