合成含對位光電性基團取代基(芴基)聚苯乙烯衍生物之立體規則性高分子:立體規則性與鏈轉移反應效率控制

The Preparation of Para-optoelectronic Groups(fluorene) containing Stereoregular Polymers of Styrene Derivative: Stereoregularity and chain transfer efficiency controls

宋學維(Shiue-Wei Sung)

指導教授 ： 蔡敬誠

國立中正大學/工學院/化學工程學系/碩士(2013年)

摘要

共軛高分子材料為近年來不僅在學術上且在工業上都相當熱門的研究課題，因其應用於有機發光二極體，太陽能電池及導電高分子材料之應用，理論上可依其結構分為主鏈共軛高分子材料及支鏈共軛高分子材料。而本研究將藉由實驗室多年來學長姐所建立的高分子合成技術以合成新型具備立體規則性支鏈共軛發光聚合物材料。
下列為合成本研究之支鏈共軛高分子材料之主要反應步驟
將苯對位位置帶有halides側鏈基的單體(4Br-S)，使用鈀金屬觸媒系統進行Suzuki 耦合反應，誘導4-溴苯乙烯單體與立體障礙較大的硼化合物進行反應，合成出苯對位位置帶有光電基團取代基之乙烯基芳香族單體4-(9,9-雙丁基-2-芴基)苯乙烯，此一結構經實驗證實具備photoluminescence效應。
使用Cp*Ti(OMe)3/MAO, Nickel acetylacetonate觸媒系統以及陰離子鏈鎖聚合反應聚合此側鏈帶有光電基團的苯乙烯衍生單體4-(9,9-雙丁基-2-芴基)苯乙烯並在Cp*Ti(OMe)3/MAO觸媒系統下以DMPVS做為鏈轉移劑下探討其選擇性鏈轉移效果的影響。將上述合成出的高分子材料進行核磁共振分析儀、調幅式微差掃描熱卡計(MDSC)實驗檢測或激發螢光光譜實驗(photoluminescence) 檢測其發光與立體規則性之性質差異。
關鍵詞:Suzuki 耦合反應、激發螢光光譜實驗、發光高分子、Cp*Ti(OMe)3/MAO、Nickel acetylacetonate、陰離子鏈鎖聚合反應

關鍵字

Nickel acetylacetonate ； Cp*Ti(OMe)3/MAO ； 激發螢光光譜實驗 ； 發光高分子 ； Suzuki 耦合反應 ； 陰離子鏈鎖聚合反應

並列摘要

Studies of Conjugated polymers have drawn tremendous research interest and industrial applications in recent years due to their potential applications in the field of organic light emitting polymers, solar cell materials and conducting polymers. In general, conjugated polymers can be divided into two categories, including main-chain and side chain conjugated polymers. In this study, we focus on the syntheses of syndiotactic polystyrene derivative based side-chain conjugated polymer, which may offer important industrial applications and unique photoluminescence properties. Three different tactic, including atactic, isotactic and syndiotactic poly-4-(9,9-dibutylfluorene-2-yl)styrene were synthesized, and their corresponding physical properties were examined. The following summarize the research work accomplished in this study:
4-(9,9-dibutylfluorene-2-yl)styrene monomer was synthesized by coupling 4-bromostyrene with aromatic boronic acid through palladium-catalyst-mediated Suzuki cross coupling reaction. The resulting 4-(9,9-dibutylfluorene-2-yl)styrene monomer exhibits light-emitting property as demonstrated by PL analyses.
Syndiotactic , Isotactic and Atactic poly-4-(9,9-dibutylfluorene-2-yl) styrene were synthesized by conducting the syndiospecific, isospecific and anionic polymerization of 4-(9,9-dibutylfluorene-2-yl)styrene in the presence of Cp*Ti(OMe)3/MAO, Nickel acetylacetonate and n-butyl lithium catalysts, respectively. In these studies, DMVPS were used as chain transfer agents to investigate its corresponding chain transfer efficiency and end-functionalization efficiency.The resulting syndiotactic, isotactic. atactic polymers were found not only to have the well-defined chemical structures but also to exhibit different light-emitting properties as demonstrated by PL analyses.

keywords: Suzuki cross coupling , light emitting polymers, PL analyses, Cp*Ti(OMe)3/MAO, Nickel Acetylacetonate, anionic chain polymerization.

並列關鍵字

Nickel acetylacetonate ； Cp*Ti(OMe)3/MAO ； photoluminescence ； light emitting polymers ； Suzuki cross coupling ； anionic chain polymerization

參考文獻

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