原位生成的鹼土金屬醇鹽催化劑對內酯單體進行開環聚合反應

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姓名

王昶琥(Chang-Hu, Wang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

原位生成的鹼土金屬醇鹽催化劑對內酯單體進行開環聚合反應

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摘要(中)

聚酯類化合物PCL和PLA是常見的內酯開環聚合產物由於其良好的生物相容性且易於降解的特性，已被廣泛應用於包裝材料及醫療用途使用。鹼土族金屬有較低的毒性、容易取得且價格便宜，適合作為催化劑在開環聚合領域中已被廣泛的使用。本研究使用鹼土族金屬 (Mg, Ca, Sr) 催化劑，在室溫下進行開環聚合反應，在加入苯甲醇作為起始劑，使催化劑在反應過程中原位生成鹼土金屬苯甲醇鹽，可以在極短的時間 (1分鐘) 內對ε-己內酯 (ε-CL)、δ-戊內酯 (δ-VL) 及 (10分鐘) 丙交酯 (L-LA) 完成單體的開環 (轉化率 > 90 %)，獲得分散性良好的PCL (最佳Đ 1.39)、PVL (最佳Đ 1.16)及PLA (最佳Đ 1.09)。我們進行了聚合反應動力學的研究，對於這些內酯單體濃度皆為二級反應，並且反應速率方面PCL Mg < Ca < Sr，而PLA Ca < Sr < Mg。這些研究成果皆顯示鹼土族金屬催化劑在溫和的條件下對開環聚合反應有優秀的催化活性，並使聚合反應保持在良好的控制下。

摘要(英)

Polyester such as PCL and PLA are common products of lactone ring-opening polymerization. Due to their good biocompatibility and ease of degradation, they have been widely used in packaging materials and medical applications. Alkaline earth metals, which have lower toxicity, are readily available, and inexpensive, suitable as catalysts and have been widely used in the field of ring-opening polymerization. In this study, we used alkaline earth metal (Mg, Ca, Sr) catalysts to conduct ring-opening polymerization reactions at room temperature. By adding benzyl alcohol as an initiator, the catalysts generated alkaline earth metal benzyl alkoxide during the reaction. This method allowed the ring-opening of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL), and (within 10 minutes) L-lactide (L-LA) , respectively to be completed in an extremely short time (1 minute), achieving conversion rates of over 90%. The resulting polymers exhibited narrow dispersity: PCL (optimal Đ 1.39), PVL (optimal Đ...), and PLA (optimal Đ 1.09). We conducted a kinetic study of the polymerization reactions, finding that the concentration of these lactone monomers followed second-order kinetics. The reaction rates were PCL Mg < Ca < Sr and PLA Ca < Sr < Mg. These research results demonstrate that alkaline earth metal catalysts exhibit excellent catalytic activity under mild conditions for ring-opening polymerization reactions and maintain good controlled polymerization.

關鍵字(中)

★ 鹼土族金屬
★ 開環聚合
★ 動力學
★ 聚內酯

關鍵字(英)

★ alkaline earth metals
★ ring-opening polymerization
★ reaction kinetics
★ Polylactone

論文目次

國立中央大學圖書館學位論文授權書 i
國家圖書館學位論文延後公開申請書 ii
論文指導教授推薦書 iii
論文口試委員審定書 iv
中文摘要 v
Abstract vi
謝誌 viii
目錄 ix
圖目錄 xii
表目錄 xv
第一章緒論 1
1-1 前言 1
1-2 內酯單體介紹 2
1-3 配位基 (HMDS)介紹 3
1-3-1 使用Free HMDS作為NCA單體聚合反應催化劑 3
1-3-2 使用HMDS衍生的催化劑聚合NCA單體 6
1-4 鹼土族金屬催化劑應用於開環聚合反應 9
1-4-1 毒性與生物相容性 9
1-5 醇鹽用於內酯聚合 13
1-6 研究目的 19
第二章實驗部分 20
2-1 鑑定儀器 20
2-2 溶劑及藥品處理 21
2-3 製備NaHMDS 23
2-4 製備Ca(HMDS)2 24
2-4-1 由CaI2製備Ca(HMDS)2 24
2-4-2 由CaCl2一鍋化製備Ca(HMDS)2 24
2-5 製備Sr(HMDS)2 25
2-6 製備Mg(HMDS)2 26
2-7 催化劑的鑑定 26
2-7-1 金屬含量滴定 26
2-7-2 HMDS含量鑑定 28
2-8 聚合反應步驟 29
2-8-1 製備終止試劑BAT 29
2-8-2 聚合反應動力學及反應時間測定 29
2-9 GPC樣品製備及處理 30
第三章結果與討論 31
3-1 以HMDS對內酯單體的開環聚合嘗試 31
3-2 Ca(HMDS)2對ε-CL開環聚合條件優化 33
3-3 Ae(HMDS)2對於ε-CL、δ-VL及γ-BL的開環聚合結果及動力學研究 36
3-4 Ca(HMDS)2對於L-LA開環聚合條件優化 43
3-5 Ae(HMDS)2對於L-LA的開環聚合結果與動力學研究 55
3-6 內酯開環的反應機構 59
第四章結論 65
參考資料 67
附錄1-NMR光譜 70
附錄2-催化劑滴定數據 92
附錄3-GPC圖譜 105
論文比對電子回條 112

參考文獻

(1) Barnes, D. K.; Galgani, F.; Thompson, R. C.; Barlaz, M. Accumulation
and Fragmentation of Plastic Debris in Global Environments. Philos. Trans.
R. Soc. B 2009, 364 (1526), 1985-1998.
(2) Geyer, R.; Jambeck, J. R.; Law, K. L. Production, Use, and Fate of All
Plastics ever Made. Sci. Adv. 2017, 3 (7), e1700782.
(3) Natta, F. J. v.; Hill, J. W.; Carothers, W. H. Studies of Polymerization
and Ring Formation. XXIII. 1 ε-Caprolactone and Its Polymers. J. Am. Chem.
Soc. 1934, 56 (2), 455-457.
(4) Woodruff, M. A.; Hutmacher, D. W. The Return of a Forgotten
Polymer—Polycaprolactone in the 21st Century. Prog. Polym. Sci. 2010, 35
(10), 1217-1256.
(5) Nevoralová, M.; Koutný, M.; Ujčić, A.; Starý, Z.; Šerá, J.; Vlková, H.;
Šlouf, M.; Fortelný, I.; Kruliš, Z. Structure Characterization and
Biodegradation Rate of Poly (ε-caprolactone)/Starch Blends. Front. Mater.
2020, 7, 141.
(6) Nampoothiri, K. M.; Nair, N. R.; John, R. P. An Overview of the Recent
Developments in Polylactide (PLA) Research. Bioresour. Technol. 2010,
101 (22), 8493-8501.
(7) Shi, C.; Quinn, E. C.; Diment, W. T.; Chen, E. Y.-X. Recyclable and (Bio)
Degradable Polyesters in a Circular Plastics Economy. Chem. Rev. 2024, 124
(7), 4393-4478.
(8) Lu, H.; Cheng, J. Hexamethyldisilazane-Mediated Controlled
110
Polymerization of α-Amino Acid N-Carboxyanhydrides. J. Am. Chem. Soc.
2007, 129 (46), 14114-14115.
(9) Lu, H.; Cheng, J. N-Trimethylsilyl Amines for Controlled Ring-Opening
Polymerization of Amino Acid N-Carboxyanhydrides and Facile End Group
Functionalization of Polypeptides. J. Am. Chem. Soc. 2008, 130 (38), 12562-
12563.
(10) Bhattacharjee, J.; Sarkar, A.; Panda, T. K. Alkali and Alkaline Earth
Metal Complexes as Versatile Catalysts for Ring‐Opening Polymerization
of Cyclic Esters. Chem. Rec. 2021, 21 (8), 1898-1911.
(11) Tong, R.; Cheng, J. Paclitaxel‐Initiated, Controlled Polymerization of
Lactide for the Formulation of Polymeric Nanoparticulate Delivery Vehicles.
Angew. Chem. Int. Ed. 2008, 47 (26), 4830-4834.
(12) Zhong, Z.; Dijkstra, P. J.; Birg, C.; Westerhausen, M.; Feijen, J. A Novel
and Versatile Calcium-Based Initiator System for the Ring-Opening
Polymerization of Cyclic Esters. Macromolecules 2001, 34 (12), 3863-3868.
(13) Zhou, X.; Liu, Q.; Xu, G.; Yang, R.; Sun, H.; Wang, Q. Chemical
Upcycling of Poly (lactide) Plastic Waste to Lactate Ester, Lactide and New
Poly (lactide) Under Mg-Catalysis Condition. Chin. Chem. Lett. 2023, 34
(10), 108158.
(14) Bandelli, D.; Weber, C.; Schubert, U. S. Strontium Isopropoxide: A
Highly Active Catalyst for the Ring‐Opening Polymerization of Lactide and
Various Lactones. Macromol. Rapid Commun. 2019, 40 (20), 1900306.
(15) 贺向民 . Method for Preparing Sodium Bis(trimethylsilyl)amide
Solution. China CN101492466, 2009.
111
(16) Brady, E. D.; Hanusa, T. P.; Pink, M.; Young, V. G. The First
Noncoordinated Phosphonium Diylide,[Me2P(C13H8)2]-, and Its Ylidic and
Cationic Counterparts: Synthesis, Structural Characterization, and
Interaction with the Heavy Group 2 Metals. Inorg. Chem. 2000, 39 (26),
6028-6037.
(17) Love, B. E.; Jones, E. G. The Use of Salicylaldehyde Phenylhydrazone
as an Indicator for the Titration of Organometallic Reagents. J. Org. Chem.
1999, 64 (10), 3755-3756.
(18) Li, L.; Cen, J.; Pan, W.; Zhang, Y.; Leng, X.; Tan, Z.; Yin, H.; Liu, S.
Synthesis of Polypeptides with High-Fidelity Terminal Functionalities
Under NCA Monomer-Starved Conditions. Research 2021.
(19) Wang, M.; Ding, Z.; Wang, B.; Li, Y. (Bipyridine bisphenolate)-
Aluminum/Onium Salt Pair: a Highly Active Binary Catalyst for RingOpening Polymerization of Lactide with Improved Thermostability and
Protic Tolerance. Polym. Chem. 2023, 14 (1), 45-54.
(20) Wu, J.-C.; Huang, B.-H.; Hsueh, M.-L.; Lai, S.-L.; Lin, C.-C. RingOpening Polymerization of Lactide Initiated by Magnesium and Zinc
Alkoxides. Polymer 2005, 46 (23), 9784-9792.

指導教授

吳國暉(wukuohui)

審核日期

2024-8-20

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