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標題: 雙巨環形醯基尿素之合成與其自我聚合應用
Synthesis and Self-polymerization of Bismacrocyclic acylureas
作者: 曾淑玲
Tzeng, Su-Ling
關鍵字: macrocyclic CDI;巨環形碳二亞胺;intramolecular cyclization;pseudo high dilution synthesis;bis-macrocyclic acylurea;blocked isocyanate;moisture curing;分子內環化反應;擬高稀法;雙巨環型醯基尿素;封閉型異氰酸鹽;濕氣硬化
出版社: 化學工程學系所
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在合成巨環形碳二亞胺(macrocyclic carbodiimide,MC-CDI)的程序研究過程中,1,3-dimethyl-3-phospholene oxide (DMPO)、3-methyl-1-phenyl-2-phospholene 1-oxide (MPPO)及triphenylarsine oxide (TPAO) 這三種異氰酸鹽預聚物之環閉合劑催化劑,被用來鑑別合成碳二亞胺(MC-CDI)之合成效率。預聚物由甲苯二異氰酸鹽(2,4-Toluene diisocyanate,2,4-TDI)與分子量700之聚異丙二醇中反應製得。在合成MC-CDI環化反應中,以擬高稀(pseudo high dilution)合成法在濃度約8 g/ L甲苯時,TPAO催化劑可達到高選擇率(95%)自我環化的優勢。
單環MC-CDI可進一步藉由管柱層析,從副產物及高分子量混合物中純化出來,並再進一步與芳香族二元酸,如聚醚二元酸[poly(oxypropylene) bis(trimellitic imide acid),POTDA],可順利地反應獲得高產率的雙巨環形醯基尿素(bis-macrocyclic acylurea,MC2-ACU)。MC2-ACU亦可直接由Crude MC-CDI與POTDA或間苯二甲酸(isophthalic acid,IPA)反應獲得。
由於MC2-ACU在120℃時,具有熱裂解開環再生異氰酸鹽之特性,因此可視為一種封閉型異氰酸鹽(blocked isocyanate),並依此獨特的性質,可藉由加熱MC2-ACU開環,以濕氣硬化的方式進行自我聚合,獲得光滑的薄膜。這過程可一步獲得高分子量的polyamide- imide-urethane-urea 和polyamide-urethane薄膜。

On the process refinement study for making macrocyclic carbodiimide (MC-CDI), several carbodiimide catalysts, such as 1,3-dimethyl-3- phospholene 1-oxide (DMPO), 3-methyl-1-phenyl-2-phospholene 1-oxide (MPPO), and triphenylarsine oxide (TPAO) were screened to differentiate their effectiveness as ring-closure agents from the isocyanate prepolymer made from 2,4-toluene diisocyanate (2,4-TDI) and propoxylated polyether diol of 700 molecular weight. It was found that TPAO has the advantage in forming MC-CDI under pseudo high dilution of 8 g/ L in toluene solution with a high selectivity (95%) in ring-formation.
Pure MC-CDI could be further purified by column chromatogram to separate it from by-products and higher molecular weight components. Upon treatment of aromatic dicarboxylic acid such as poly(oxypropylene) bis(trimellitic imide acid) (POTDA), MC-CDI was smoothly converted into bis-macrocyclic acylurea (MC2-ACU) in high yield. Alternatively, MC2-ACU could also be prepared directly from crude MC-CDI and two aryl diacids, POTDA or isophthalic acid (IPA) .
MC2-ACU can be regarded as a blocked di-isocyanate precursor because it was demonstrated to undergo a ring-opening reaction in generation of di-isocyanate upon thermolysis at 120℃. Because of this unique property, a self ring-opening polymerization was carried out by moisture-curing of the heated MC2-ACU in neat thin-film. This process resulted in formation of a thin-film of polyamide-imide-urethane-urea and polyamide-urethane of high molecular weight in one-step.
With our continuous process improvements in synthesis of 2,4-TDI prepolymers and MC-CDI, MC2-ACU can be available as a blocked isocyanate precursor in quantity for future applications in many moderate- temperature curing reactions.
其他識別: U0005-1508200817272900
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