- 學位論文
商用自身終止超分歧寡聚物合成優化之核磁共振研究
The optimized commercial STOBA synthesis by NMR investigation
摘要
自身終止超分歧寡聚物 (self-terminated oligomers with hyper-branched architecture，簡稱為 STOBA) 為一種智慧型的功能性高分子聚合物，其用途之一是作為鋰離子電池的安全添加劑以避免熱爆炸發生。 我們運用多核種、多維度之 NMR 相關脈衝程序，依序對下列主題做 NMR 的研究：(一) STOBA 原料物雙馬來醯亞胺(4,4’-Bismaleimidodi-phenylmethane，簡稱為 BMI1000) 的衍生物 (BMI2300) 與巴比妥酸 (Barbituric Acid，簡稱為 BTA) 以及溶劑甲基吡咯烷酮 (N-Methyl-2-pyrrolidone，簡寫為 NMP) 定義其結構上的標示並辨識出其相對應的訊號以確認反應物樣品的純度及反應過程中定量分析之用；(二) 利用一維氫譜測量各原料物在 130 ºC 下的自身反應，並依據其積分比例來定量計算在聚合反應時反應物的自身反應消耗情形及定性確認反應物活性基團的位置；(三) 推測 STOBA 合成反應在化學動力學的可能反應機制及其鍵結行為，並藉此推測 STOBA 的分子結構與其作為鋰離子電池安全添加劑之安全作動行為機制。 藉由 NMR 分析並佐以 SAXS, SEM, GPC 的實驗結果，我們證實 STOBA 合成的主要反應機制包含 Michael addition 與 radical homopolymerization 兩種。在不同的反應溫度下，兩種反應機制互相競爭。隨時間的演化，生成物會依序由寡聚體、初級結構 (primary structure)、進而聚集成類球形樹枝狀實用的二級 STOBA 結構 (secondary structure)。
並列摘要
STOBA (self-terminated oligomers with hyper-branched architecture) is a smart functional polymer, one of its use is as an additive safety of lithium-ion battery to avoid thermal explosion. We use multi- nuclide and multi-dimensional NMR pulse sequences, sequential do NMR study of the following topics: (i) labeling and assigning the raw material of STOBA: BMI2300, the derivatives of BMI1000 (4,4'-Bismaleimidodi-phenylmethane), BTA (Barbituric Acid) and solvent NMP (N-Methyl-2-pyrrolidone) to confirm the purity of reactants and analysis quantitatively during the reaction.(ii) using the one-dimensional 1H NMR spectrum of each raw material at 130 ºC self-reaction, and based on its integral ratio to quantitative calculation in the polymerization reaction of self-reactive reactant consumption situation and qualitative confirm the location of the reactants active group.(iii) surmising the possible reaction mechanism and the bonding of reactants in STOBA synthesis reaction in chemical kinetics in order to surmise STOBA molecular structure and the safety mechanism actuation behavior when STOBA as an additive safety of lithium-ion battery. According to NMR and SAXS, SEM, GPC supplemented, we confirmed that STOBA synthesis of the main reaction mechanism consists of two kinds: Michael addition reaction and homopolymerization radical reaction.Two reaction mechanisms competing under different reaction temperature. With the evolution of time, the product will be sequentially from the oligomers, the primary structure, and then gathered into a practical STOBA spherical-like dendrimer secondary structure.