含芘分子起始劑在光誘發原子轉移自由基聚合之應用與含芘分子之聚苯乙烯的螢光放光增強現象

Pyrene Based Initiator in Photo-induced ATRP and Persistently Enhanced Fluorescence Observed from Poly(styrene) with Pyrene Chromophore

蘇俊憲(Su, Chun Hsien)

指導教授 ： 彭之皓

國立清華大學/理學院/化學系/碩士(2015年)

https://doi.org/10.6843/NTHU.2015.00090

摘要

本論文大致分為三部分，第一部份是先合成含有芘發光團的分子來作為ATRP或是Photo-induced ATRP的起始劑。經由聚合反應可以獲得良好控制的含芘螢光高分子 (Mw / Mn = 1.20 ~ 1.30)，或是可發螢光之嵌段共聚物。光誘發的 ATRP 方法，可使用在不同的單體 (MMA, MA, St) 上，並有高效率或是節能等優勢。在光誘發之ATRP 中，所需的能量來源甚至可以只使用低功率手持式的紫外燈便可取代傳統使用的油浴或是加熱等方法。
在第二部份裡,光誘發的聚合反應中發現了光聚合之含芘聚苯乙烯的螢光放光現象較其他使用同製程之聚合物更高。為了探討其放光增強的原因，聚合物的單體種類、發光團種類、合成方法、結構與穩定性、及溶劑比例都進行調整與比較。發現光聚合得到之含芘聚苯乙烯的螢光強度確實高於其他含芘之聚合物，且螢光性質產生些許紅位移現象，其原因並非分子穩定性、立體異構性等因素，也與芘發光團和苯乙烯溶劑的選擇有關，其螢光強度上升幅度也和苯乙烯溶劑的比例成正比關係。
第三部份,則把各種含芘之螢光聚合物藉由通過陽極氧化鋁模板來形成奈米中空管柱結構。利用掃描式穿隧顯微鏡可證實聚合物之奈米中空管柱結構。結構與螢光性質的關係同時也被探討。

關鍵字

原子轉移自由基聚合反應 ； 光誘發原子轉移自由基聚合反應 ； 苯乙烯 ； 螢光 ； 螢光聚合物 ； 奈米中空管柱 ； 陽極氧化鋁

並列摘要

Chromophoric initiator containing pyrene moiety was synthesized and was used to the normal and photo-induced ATRP of various monomers to obtain the flourscent polymer. These well-controlled dye-labeled polymer showed a low polydispersity (Mw / Mn = 1.20 ~ 1.30), and could form the diblock copolymers.
Photo-induced or Photo-mediated ATRP was performed in our study. Photo-induced ATRP is an efficient or economical method for methyl acrylate, methyl methacrylate and styrene polymerization. The photo-mediated polymerization could use the handheld UV light as the low energy source to replace the traditional oil bath or the high temperature condition.
Besides, during the photo-induced ATRP process we found the poly(styrene) had the strongest fluorescence than other polymers. For this reason, we compared the fluorescence of dye-labeled polymer by ATRP and photo-induced ATRP. Moreover we designed some control experiments to illustrate and explain the strongly fluorescent effect in poly(styrene) by photo-induced ATRP.
Meanwhile, we used the homo or diblock copolymer with chromophore to form the nanotube polymer structure by AAO (anodic aluminum oxide) template. The nanotube structure could be observed by the SEM (Scanning electron microscopy) and the fluorescence of nanotube polymer structure was also discussed.

並列關鍵字

ATRP ； photo-induced ATRP ； Styrene ； Fluorescence ； dye-labeled polymer ； nanotube structure ； AAO

參考文獻

3. Yamago, S.; Iida, K.; Yoshida, J.-i., J. Am. Chem. Soc. 2002, 124, 2874-2875.

6. Perrier, S.; Takolpuckdee, P., J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5347-5393.

10. Percec, V.; Barboiu, B., Macromolecules 1995, 28, 7970-7972.

11. Matyjaszewski, K.; Xia, J., Chem. Rev. 2001, 101, 2921-2990.

12. Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T., Macromolecules 1995, 28, 1721-1723.