具有可交聯和可接枝特性之氮矽三環基團用於製備高穩定性雙離子水凝膠生醫塗層;Ultra-stable Zwitterionic Hydrogel Coating Using Zwitterionic Copolymers with Crosslinkable and Graftable Silatrane Moiety

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題名:	具有可交聯和可接枝特性之氮矽三環基團用於製備高穩定性雙離子水凝膠生醫塗層;Ultra-stable Zwitterionic Hydrogel Coating Using Zwitterionic Copolymers with Crosslinkable and Graftable Silatrane Moiety
作者:	陳芝伃;Chen, Chih-Yu
貢獻者:	化學工程與材料工程學系
關鍵詞:	兩性離子共聚物;潤滑;抗沾黏;穩定性;可控矽烷化;zwitterionic copolymer;lubrication;antifouling properties;stability;control silanization;silatrane
日期:	2025-07-22
上傳時間:	2025-10-17 11:24:52 (UTC+8)
出版者:	國立中央大學
摘要:	兩性離子化 (Zwitterionization) 是一種表面修飾技術，利用雙離子材料來達到超親水性、抗沾黏和潤滑效果。然而，雙離子塗層在表面的穩定性和耐久性在醫療器械和長期植入裝置等應用中仍面臨挑戰。特別是在水溶液中，高度膨脹和延展的聚合物鏈容易受到外部的應力破壞。因此在本研究中，我們開發出一種新型含氮矽三環 (Silatrane) 結構之雙離子共聚物，並應用於氧化物基材表面的水凝膠生醫塗層，藉以提升其長期穩定性與耐久性。甲基丙烯酸酯氮矽三環 (Methylacrylate silatrane, MAST) 是一種具備可聚合、可交聯與可接枝性的功能性單體，可作為合成聚合物中的結構單元。藉由雙離子單體 2-甲基丙烯酰氧乙基磷酸膽鹼 (2-methacryloyloxyethyl phosphorylcholine, MPC) 與 MAST 聚合後，以獲得可用於表面沉積和修飾的塗層材料 (MAST-co-MPC)。常用的商用矽烷官能基材料甲基丙烯酸-3-(三甲氧基甲硅烷基)丙酯(3-(Trimethoxysilyl)propyl methacrylate, TMSPMA) 亦作為單體，以合成塗層共聚物 (TMSPMA-co-MPC)，並將兩者之穩定性及塗層效果進行比較。由於氮矽三環的化學結構具有高度化學穩定性，使 MAST 可實現「可控矽烷化」，從而精確接枝聚合物鏈至氧化矽表面。並且水解後的氮矽三環會轉化為矽醇基團，進一步通過縮合和交聯反應形成聚合物網絡，顯著提高了水凝膠塗層的穩定性。我們進一步利用流變儀測試塗層的耐久性及潤滑性能。塗層的功能性則透過表面水合能力及抗蛋白 / 抗菌貼附性來表徵。此外，MAST-co-MPC高分子也被修飾在不鏽鋼、氧化矽、聚苯乙烯、聚氨酯、鎳鈦合金和鋁等多種氧化物表面，展現了其廣泛的應用性。總結來說，我們成功開發了一種基於氮矽三環類化合物和雙離子化學特性，可應用於多種基材和廣泛領域的穩定且耐久醫用塗層材料。;Zwitterionization is a surface modification technique that employs zwitterionic materials to achieve superhydrophilicity, antifouling properties, and lubrication. However, the stability and durability of zwitterionic coatings on surfaces remain a critical challenge for their application in medical apparatus and long-acting devices. Particularly, the highly swollen and stretched polymer chains in an aqueous solution can be easily destroyed by external stress. Herein, we propose a new silatrane-containing zwitterionic copolymer for the development of medical hydrogel coatings on oxide surfaces for long-term effectiveness and durability. Methylacrylate silatrane (MAST) is a polymerizable, crosslinkable and graftable building block for synthesis of the copolymers. Zwitterionic monomer of 2-methacryloyloxyethyl phosphorylcholine (MPC) was applied to copolymerize with MAST to obtain the coating materials (MAST-co-MPC) for surface deposition and modification. Commercial available 3-(Trimethoxysilyl)propyl methacrylate (TMSPMA) was used as a monomer for the develop the coating copolymers (TMSPMA-co-MPC) to compare the stability and coating effectiveness. Because of highly chemical stability of silatrane chemistry, MAST enables “control silanization” to precisely graft the polymer chains on silicon oxide. In addition, the hydrolyzed silatrane turns to silanol groups to undergo condensation and crosslinking to form polymer networks. The stability of the hydrogel coatings were significantly improved, and durability and lubrication of the coatings were further examined using rheometer. The functionalities of the medical coatings were characterized in terms of surface hydration and anti-protein/-bacterial adsorption. Moreover, the MAST-co-MPC was deposited on various oxide surfaces, such as stainless steel, oxided silicone/polystyrene/polyurethane, nitinol and aluminum to demonstrate its versatility. In summary, we successfully developed a reliable and durable medical coating materials based on silatrane and zwitterionic chemistries for a wide spectrum of substrates and applications.
顯示於類別:	[化學工程與材料工程研究所] 博碩士論文

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