本研究以多官能基的米氏酸衍生物製備生物可降解的類玻璃聚酯，米氏酸 (Meldrum’s acid, MA) 在高溫下熱裂解產生烯酮 (ketene) 官能基，與羥基反應，生成動態共價酯鍵，製備類玻璃聚酯。
第一部分透過有機合成的方式，成功合成雙官能基的米氏酸衍生物MABMA。
第二部分以傳統逐步聚合反應，以癸二酸(sebacic acid)與甘油(glycerol)作為原料，進行A2+B3系統的縮合聚合反應，成功製備聚癸二酸甘油酯 (poly(glycerol sebacate), PGS)。
第三部分因羥基能催化米氏酸開環，在較低溫的環境產生烯酮官能基，以帶有羥基的聚癸二酸甘油酯過量進料的方式，預期製備動態可逆的酯鍵，在高分子網絡具有羥基可催化酯交換。將所合成之MABMA，作為PGS的交聯劑，改變米氏酸對羥基當量比例，改變羥基在高分子網絡中的含量，製備兩種交聯聚酯CR-MABMA-PGS-1.5、CR-MABMA-PGS-2，並證明其具有類玻璃聚酯的酯交換特性、可回收性、二次加工特性與生物可降解性。

In this study, biodegradable polyester vitrimers were prepared by multifunctional Meldrum’s acid derivatives. The ketene generated by thermal pyrolysis of Meldrum’s acid reacted with hydroxyl group to form dynamic covalent ester bonds in order to prepare polyester vitrimers.
The first part, a bifunctional Meldrum’s acid derivative MABMA was successfully synthesized through organic synthesis.
In the second part, it involved a traditional step-growth polymerization reaction. Sebacic acid and glycerol were employed as raw materials to conduct the A2+B3 type condensation polymerization reaction. Poly(glycerol sebacate) (PGS) was successfully prepared.
In the third part, the Meldrum’s acid can generate ketene functional groups at lower temperature because the hydroxyl group can catalyze the ring-opening of Meldrum’s acid. By the method of excessive feeding of PGS, the dynamic covalent ester bonds were prepared, and the excess hydroxyl groups can catalyze transesterification in the polymer network. The synthesized MABMA were utilized as crosslinking agent of PGS. By changing the ratio of Meldrum’s acid to hydroxyl group equivalents to change the content of hydroxyl groups in the polymer network. It is planned to prepare a variety of crosslinked polyesters, and prove that they have transesterification properties, self-healing, and recyclability and biodegradability.

摘要-----i
Abstract-----ii
圖目錄-----vii
表目錄-----xiv
第一章 緒論-----1
1-1 前言-----1
1-2 熱固性高分子-----3
1-3 類玻璃高分子(Vitrimers)-----4
1-4 研究動機-----8
第二章 文獻回顧-----9
2-1 動態共價鍵種類-----9
2-2 類玻璃高分子合成-----13
2-2-1 類玻璃聚酯合成-小分子聚合-----15
2-2-2 類玻璃聚酯合成-小分子含有動態鍵結-----16
2-2-3 類玻璃聚酯合成-交聯熱塑性高分子-----17
2-3 動態酯鍵合成-----18
2-4 米氏酸衍生物合成聚酯類-----19
2-5 米氏酸衍生物合成類玻璃聚酯-----21
2-6 生物可降解高分子-----23
2-7 生物可降解類玻璃高分子合成-----24
2-8 研究方法-----28
第三章 實驗方法-----29
3-1 實驗藥品-----29
3-2 實驗儀器-----33
3-3 實驗步驟-----36
3-3-1 具雙官能基的米氏酸芳香族單體合成(MABMA)-----36
3-3-2 聚癸二酸甘油酯合成(PGS)-----37
3-3-3 緻密交聯聚酯高分子CR-MABMA-PGS-1.5製備-----37
3-3-4 緻密交聯聚酯高分子CR-MABMA-PGS-2製備-----38
3-3-5 緻密交聯聚酯高分子(CR-MABMA-PGS-1.5, CR-MABMA-PGS-2)之物理回收條件-----40
3-3-6 緻密交聯聚酯高分子(CR-MABMA-PGS-1.5, CR-MABMA-PGS-2)之生物降解能力測試-----41
第四章 結果與討論-----42
4-1 具雙官能基的米氏酸芳香族單體-----42
4-1-1 具雙官能基的米氏酸芳香族(MABMA)單體結構鑑定-----42
4-1-2 具雙官能基的米氏酸芳香族單體熱性質分析-----45
4-2 聚癸二酸甘油酯-----47
4-2-1聚癸二酸甘油酯(PGS)預聚物結構鑑定-----47
4-3 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯-----51
4-3-1 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯(CR-MABMA-PGS-1.5, CR-MABMA-PGS-2)之合成與結構鑑定-----51
4-3-2 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之熱性質-----55
4-3-3 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之機械性質-----58
4-3-4 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之凝膠比例與溶脹率-----62
4-3-5 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之頻率掃描測試-----64
4-3-6 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之接觸角測試-----65
4-3-7 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之吸水測試-----66
4-4 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之回收能力-----67
4-4-1 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之應力鬆弛-----67
4-4-2 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之蠕變測試-----72
4-4-2 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之黏度測試-----74
4-4-3 回收交聯聚酯之回收條件與結構鑑定-----75
4-4-4 回收交聯聚酯之熱性質-----77
4-4-5 回收交聯聚酯之機械性質-----79
4-4-6 回收交聯聚酯之凝膠比例與溶脹率-----87
4-4-7 回收交聯聚酯之應力鬆弛-----89
4-4-8 回收交聯聚酯之截面平整度-----92
4-5 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之熱響應能力-----95
4-6 交聯芳香族雙米氏酸-聚癸二酸甘油酯聚酯之生物降解能力-----101
第五章 結論-----103
第六章 參考文獻-----105

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