共軛棒桿-線團嵌段共聚合體之合成與物性研究

Studies on the synthesis and physical properties of conjugated rod-coil block copolymer

黃振勛(Jenn-Shiun Huang)

指導教授 ： 廖建勛

元智大學/工程學院/化學工程與材料科學學系/碩士(2003年)

摘要

本研究藉由2,7-二溴-9,9-二辛烷基茀、2,5-二溴-3-辛烷基噻吩兩種雙溴基取代的芳香族單體分別與TEMPO-capped單體，同時進行共軛高分子嵌段（B）的偶合聚合反應與機能性苯乙烯（A）單體的活性自由基聚合反應，藉由三種不同的嵌段比例（3-2-3、1-1-1、1-2-1）A-B-A構形的共軛棒桿-線團嵌段共聚合體，以NMR、FT-IR、GPC作結構鑑定，UV-Vis、PL光譜及TGA、DSC的光、熱穩定等物性分析，並經由AFM的分析探討嵌段共聚合體的表面形態。
藉由UV-Vis的分析瞭解到以茀為主體的嵌段共聚合體，因結構中π-堆疊的結果使得吸收帶較為寬廣，由於茀為一良好的藍色發光性材料，因此在PL的分析中可以看到418nm處含茀主體的共聚合體所具有的藍色發光放射峰，然而，含噻吩主體的聚合體因本身材料紅位移的影響，其吸收峰波長較含茀的共聚合體長，而其螢光放射峰則位於541nm長波長處，此外，共聚合體會因分子中苯乙烯嵌段比例的降低促使其熱穩定性的降低；在材料的表面形態分析方面，藉由不同的苯乙烯嵌段比使得高分子材料產生如小島、雙連續等不同的形態，最後，替換苯乙烯改以共聚合三苯基胺（triphenylamine，TPA）衍生物，探討其材料的光、熱穩定等物性，並作一分析、比較。

關鍵字

嵌段共聚合體 ； 茀 ； 活性自由基聚合

並列摘要

The one-pot synthesis of coil-rod-coil A-B-A tri-block copolymers with various mole ratios were performed in this study. The rod conjugated blocks proceed with the coupling reaction of aromatic monomer of 2,7-dibromo-9,9’-dioctylfluorene or 2,5-dibromo-3-
octylthiophene, where coil blocks were initiated by living free radical polymerization of styrene or vinyl triphenylamine with TEMPO-capper. The structures of tri-block copolymers were characterized by NMR spectra, FT-IR spectra, and GPC analysis. In addition, the tri-block copolymers’ optical properties by UV-vis and PL spectra, thermal properties by TGA and DSC, and morphology analysis by AFM were also conducted to correlate with the structure characteristics.
According to the analysis of optical properties, PS-PFO-PS exhibits a broad electronic absorption due to the p-stacking structure along with an intense blue emission at 418 nm. PS-P3OT-PS shows a red-shift UV-vis absorption and a PL emission at 541 nm. The thermal stabilities of tri-block copolymers decrease with decreasing PS block length. Miscellaneous morphology of cast thin films were correlated with the molar portion of coil segments.

並列關鍵字

block copolymer ； fluorene ； living free radical polymerization

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