利用穩定自由基聚合法製備氧化還原感測性薄膜

本研究利用穩定自由基法合成聚4-氯甲基苯乙烯(polychloromethylstyrene, PCMS)，並利用具有生物活性的尼可丁醇醯胺(nicotinamide)進行改質反應，合成出具有離子性且具氧化還原反應的高分子q-PCMS，再分別以環氧樹脂或PVA為基材分別製備高分子複合膜，分別以氧化劑(H202)以及還原劑(H2S2O3)探討測試所製備出的兩種不同類型之複合膜。環氧樹脂複合膜主要是針對其接觸角作探討，將氧化還原劑液滴滴於環氧樹脂複合膜表面，因為q-PCMS本身具有氧化還原的功能，因此不同濃度的氧化還原劑會影響複合膜表面上的接觸角的變化；另一方面以q-PCMS-b-PS團鏈共聚物製備PVA複合薄膜，也是以不同濃度之氧化還原劑來做測試，量測吸收高度對時間的變化性。而PVA複合膜由於PVA本身據有吸水的特性，因此則是針對含氧化劑或還原劑的吸收速率來作探討。結果顯示，所合成出來的PCMS其分子量分佈能控制在約1.1~1.2左右。以氧化還原測試環氧樹脂複合膜，當還原劑濃度提升，則接觸角則漸減；相反的氧化劑濃度漸增，接觸角則明顯增大。PVA複合膜當提高還原劑濃度測試時，複合膜吸收速率則增加，當改以含氧化劑液滴時，複合膜吸收速率則相對的減少。推測是還原劑H2S2O3與高分子之nicotinamide官能基反應，加速液滴之滲透所造成。而q-PCMS-b-PS所製備的薄膜吸收液滴其高度的變化性則是高於q-PCMS所製備的薄膜。內文中有以相位差顯微鏡觀察到高分子鏈因接觸還原劑H2S2O3則內縮，氧化劑則展開的情形。預期可作為修飾電極等生化感測材料。

關鍵字

穩定自由基聚合反應；氧化還原；功能性薄膜

並列摘要

Polychloromethylstyrene, PCMS, macro-initiators were synthesized by a stable free radical polymerizations in the presence of 2,2’,6,6’-teramethyl-1-piperidinyloxy (TEMPO) and benzoyl peroxide initiator (BPO); then the TEMPO-capped PCMS were extended by polymerization with styrene monomers to synthesize PCMS-b-PS block copolymers. The PCMS and block copolymers were further modified by nicotinamide to prepare quaternized PCMS, q-PCMS, and q-PCMS-b-PS block copolymers. The polymers were further blended with PVA in water, and the mixture was casting on a glass slide and dried to form a film. The absorption of a drop of solution with oxidant or reductant by the film was observed by an optical microscope. It was found that the rate of absorption depended significantly upon the oxidant and reduced state of the drop. The rate is faster under higher concentration of reductant, but is very slow in more oxidant state. The oxidoreduction property of the film made of the q-PCMS-b-PS block copolymers is more sensitive than that of q-PCMS homopolymers.

並列關鍵字

living free-radical polymerization ； oxidoreduction-sensitive ； polychloromethylstyrene

參考文獻

[1] Schneider M, Mulhaupt R; "Living dispersion polymeriation of styrene in the presence of polysturne-block-poly(4-trimethylsilsturn)" . Polymer Bulletin, 32, 545 (1994).

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[4] Otsu T,Matsunaga T,Kuriyama A, Yoshida M; "Living radical polymerization through the use of iniferters. Controlled synthesis of polymers", European Polymer Journal 25, 643 (1989)

[5] Schneider M, Mulhaupt R; "Living dispersion polymeriation of styrene in the presence of polysturne-block-poly(4-trimethylsilsturne) ", Polymer Bulletin 32,.545 (1994).

國際替代計量

利用穩定自由基聚合法製備氧化還原感測性薄膜

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