鈷調控自由基聚合反應：從調控劑與機制的研究到材料應用

Cobalt Mediated Radical Polymerization: from Catalysts and Mechanism Studies to Materials Applications

王富生(Wang, Fu Sheng)

指導教授 ： 彭之皓

國立清華大學/理學院/化學系所/博士(2017年)

摘要

鈷調控自由基聚合反應是一種活性自由基聚合反應。其是少數能有效的控制乙烯基酯單體類的活性自由基聚合反應。這份研究聚焦在鈷調控自由基聚合反應並能分成三個部分。在第一章我們利用鍊延伸反應來驗證三種鈷錯合物在醋酸乙烯酯的聚合反應中是經由何種路徑。同時，我們也測量了不同鈷錯合物在六十度下對丙烯酸甲酯進行活性聚合反應時的平衡常數與該鈷錯合物的半波電位之間的關係。接著我們提出了一個反應模型去描述等能量交換反應的控制機制，並輔以模擬與實驗的數據佐證。最後我們應用鈷調控自由基聚合反應合成了聚丙烯酸與聚乙烯醇的嵌段共聚物並將它製作成膜。我們發現他有良好的力學與吸水性質。

關鍵字

活性自由基聚合反應 ； 鈷調控活性自由基聚合反應 ； 等能量練轉移 ； 材料科學

並列摘要

Cobalt mediated radical polymerization (CMRP) is a living radical polymerization method, which has been recognized as one of the most efficient way to control the polymerization of vinyl esters. This research was divided into three parts. In the first chapter we demonstrated the different controlling pathway by applying three cobalt complex in the polymerization of vinyl acetate (VAc). Also the correlation between equilibrium constant and the redox potential of the complexes was established. Next, one of the controlling pathway in CMRP, degenerative transfer (DT), was studied. We build a model to describe the DT mechanism. The model was further proven by both simulation and experimental data. In the last part, CMRP was applied to obtain hydrophilic poly(acrylic acid)-b-poly(vinyl alcohol) block copolymer. The materials were studied by thermal analysis and mechanical characterization.

並列關鍵字

living radical polymerization ； cobalt mediated radical polymerization ； degenerative transfer ； materials science

參考文獻

Chapter 1:

1. Matyjaszewski, K., Macromolecules, 2012, 45 (10), 4015-4039.

4. Destarac, M., Macromol React Eng, 2010, 4 (3-4), 165-179.

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12. Liao, C. M.; Hsu, C. C.; Wang, F. S.; Wayland, B. B.; Peng, C. H., Polymer Chemistry, 2013, 4 (10), 3098-3104.