1. 功能性高分子 PDPyMA 的合成與應用 2. 矽膠交聯之熟成控制 3. Co(Salen*) 在水相中催化之自由基聚合反應

1.Synthesis and Application of Functional Polymer –PDPyMA 2.Control of Curing Time for Siloxane Crosslinking 3.Co(Salen*) Mediated Radical Polymerization in Aqueous Phase

許修豪(Hsiu-Hao Hsu)

指導教授 ： 彭之皓

國立清華大學/理學院/化學系/碩士(2014年)

摘要

功能性高分子, “Poly Di(pyridin-2-yl)methyl acrylate” (PDPyMA),被成功的合成出來。它可以充當各種金屬的載體以進行各類型的催化反應，其中在鈴木偶聯反應中，它是個良好的載體，可以進行10次的鈴木偶聯反應催化，且每一次的反應可以維持其催化活性。但其充當載體也有條件限制，並不能在酸性或鹼性的水溶液下進行反應，否則PDPyMA會被水解成聚丙烯酸(PAA)，失去其充當載體的特性。此外，不同金屬配位上功能性單體“Di(pyridin-2-yl)methyl acrylate” (DPyMA)的晶體已被X-ray鑑定出來，包括銅金屬以及鈷金屬，以建立出不同金屬錯合物的結構資料庫。
矽氫化反應在工業上被應用在合成含碳矽高分子的材料中，在生產過程中通常會添加抑制劑，其目的在於避免在預拌過程中先行發生交聯的情況(較低溫)，但在熟成過程中(較高溫)又須短時間內達成交聯的目的，以達到迅速製成的工業要求。Dimethyl fumarate 抑制劑是個較好的選擇，其可以在預拌過程中有較長的抑制效果(8小時)，且在熟成時具有較短的熟成時間(45分鐘)。
水溶性的鈷金屬錯合物CoII(salophene)被用作控制丙烯酸和乙烯基吡啶聚合反應的催化劑。在控制丙烯酸聚合的表現上，由於丙烯酸上的羥基會影響CoII(salophene)對於聚合的調控，所以其控制效果不如預期。而在控制乙烯基吡啶聚合表現中，可藉由使用1,1,1,3,3,3-六氟代-2-丙醇，這種會和乙烯基吡啶形成氫鍵的溶劑來減少吡啶配位到CoII(salophene)的情形，以達到較好的聚合控制效果。

關鍵字

功能性高分子 ； 矽氫化反應 ； 可控自由基聚合

並列摘要

Functional polymer, “Poly Di(pyridin-2-yl)methyl acrylate” (PDPyMA) was synthesized successfully, which could be served as supporters for different metals to do different catalytic reactions. In the reaction of suzuki-miyaura coupling, it could be a good supporter for ten cycles, with low yield subtraction at every circle. The condition of catalytic reactions must “not” in acid/basic aqueous, or the functional polymer“ PDPyMA” would be hydrolysis into poly acrylic acid (PAA) losing the function of being supporters for metals. Different metals including copper and cobalt metals coordinated to functional monomer “Di(pyridin-2-yl)methyl acrylate” (DPyMA) were characterized by X-ray in order to build up database of different structures of complexes.
Hydrosilylation is widely used industrially for the preparation of monomers with silicon-carbon bonds and for producing crosslinked polymers. Inhibitors are often used in industry to control the platinum-mediated addition reaction of curable systems. The addition of inhibitors prevents hydrosilylation at premix period (low temperature) while permitting rapid reaction at elevated temperature (Curing period). Dimethyl fumarate would be a good candidate for company with longer premix time (8 hours) and shorter curing time (45 minutes).
Water soluble CoII(salophene) complexes was used to do acrylic acid and 4-vinyl pyridine controlled radical polymerization. The effect of controlling acrylic acid polymerization was not as good as I expected. CoII(salophene) would be affected by hydroxyl of acrylic acid and led to poor control. In the 4-vinyl pyridine controlled radical polymerization, 1, 1, 1, 3, 3, 3-hexafluoro-2-propanol was used as solvent, which can interact with 4-vinyl pyridine via hydrogen bonding and reduce the phenomenon of binding to the CoII(salophene) catalyst.

並列關鍵字

functional polymer ； Hydrosilylation ； controlled radical polymerization

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