樹枝狀光硬化水性PU壓克力樹脂之合成與光硬化動力學及物性探討

The study on Synthesis、Kintiecs and Physical Properties of UV curing Type Waterborne Polyurethane Acrylate Dendrimer

林玠志(Jie-Jhih lin)

指導教授 ： 芮祥鵬

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2012年)

摘要

本實驗將具有高度分支球型結構的樹枝狀高分子(Dendrimer)作為核心，並將末端以不同比例接枝上聚氨酯聚丙烯酸酯，合成出不同末端PU官能基數量的聚氨酯水性壓克力樹狀高分子(Waterborne PU-acrylate Dendrimer)。包含了TMDI和PPDI兩個系統，反應過程中以傅利葉紅外線光譜儀(FT-IR)及核磁共振光譜儀(H-NMR)鑑定其結構，以確定接枝上預期的結構。本實驗將親水基與PU官能基以14:5、10:9、6:13之比例接枝，加入不同之光起始劑濃度0.5、1、3、5、7%，環境溫度分別在20、40、60、80℃下，以紫外光進行照射使其光固化(UV Curing)，觀察檢測熱流質變化儀器是使用DPA(Double Beam Photocalorimetric Accessory)，探討其光固化動力學(kinetic)之反應級數(reaction order)、反應速率與轉化率(conversion)之趨勢變化。由實驗結果發現加入的光起始劑增加至最佳濃度前，轉化率、反應級數及速率都會隨著添加之光起始劑濃度增加而上升，達到最佳濃度後其質皆會有下降的現象，推測因為光起始劑大量的自由基自我碰撞導致有下降的其況。而隨著環境溫度改變，隨溫度升高轉化率、反應級數及速率都會上升，但到了80℃時，反應級數與速率卻有下降的情況，推測是因為高溫環境下破壞了光起始劑結構，導是光固化的反應速率下降。

關鍵字

樹枝狀高分子 ； 動力學 ； 光固化 ； 轉化率 ； 動力學常數

並列摘要

The polymer used in this study is PU-acrylate dendrimer with different numbers of functional groups. It contains two systems: PPDI and Trimethyl-1,6- diisocyanatohexane (mixture of 2,2,4- and 2,4,4-isomers) system; with five, nine and thirteen functional groups respectively. In the course of the reaction, the resin was characterized by Fourier Transform Infrared Spectroscopy (FTIR) and H-NMR respectively. A series of results were concluded after the polymer exposed to UV-light. The dendrimer was added into the solution with different concentration of Photoinitiator (0.5, 1, 3, 5, 7%) and under various temperature(20, 40, 60, 80°C), respectively in order to explore the effects of UV-curing kinetic and conversion. The major test equipment is by DPA (Double Beam Photocalorimetric Accessory).
Through the results of the experiment, we discovered that the conversion, reaction rate and reaction order all increased before the reached to the the optimal concentration of photoinitiator. After reaching the certain optimal concentration of Photoinitiator, the conversion, reaction rate and reaction order all decreased presumably due to the rapid recombination of numerous free radicals. In addition, the conversion, reaction rate and reaction order increased when the temperature increased.

並列關鍵字

kinetic ； UV curing ； conversion ； dendrimer ； reaction order

參考文獻

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