利用Buchwald-Hartwig反應及Metallocene觸媒合成對位性立體規則性發光材料

Preparation of Conjugated Amine Based Vinyl Monomers and their use in the Preparation of Stereoregular Fluorescent Polymers

謝東岳(Tung-Yueh Hsieh)

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，近年來相當熱門的研究課題，因其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。理論上共軛高分子材料可因其共軛基團的位置概分為主鏈及支鏈共軛高分子材料。而本研究則將注重於開發新型支鏈共軛高分子材料，並針對支鏈共軛高分子材料之立體規則性對發光特性之影響做深入之探討。因此，本研究將利用鈀觸媒系統(Pd(OAc)2/(2-Biphenyl)di-tert-butylphosphine)誘導4-溴苯乙烯與Pyrrole進行胺化反應，合成具共軛結構之乙烯芳胺單體，然後再利用Metallocene觸媒進行對位選擇性聚合乙烯芳胺單體，使對位性聚乙烯芳胺不但具有發光性質並具備對位立體規則性。而研究的內容則包含下列三個方向：
(Ⅰ) 利用鈀金屬觸媒，誘導帶有Halides側鏈基之單體(4-溴基苯乙烯) 進行胺化銜接反應(coupling reaction)，以合成苯乙烯對位位置具有胺類取代基之乙烯基芳香單體 1-(4-vinylphenyl)-pyrrole。
(Ⅱ) 所合成之螢光性芳胺單體可利用Metallocene (Cp*Ti(OMe)3)觸媒系統進行立體規則選擇性之聚合反應，並在反應過程中加入鏈轉移劑(dimethylphenylvinylsilane)控制高分子分子量分佈，並生成末端具備特定官能基之對位聚乙烯芳胺(e.g.,syndiotactic poly-1-(4-vinylphenyl)-pyrrole)。
(Ⅲ) 本研究中還利用AlEt3作為co-initiator將其sP4VPPy-OH末端轉換成sP4VPPy-OAlEt2之macroinitiator以進行環酯類單體L-lactide的開環聚合反應，進行第二段嵌段高分子的鏈成長反應以合成出sP4VPPy-b-PLLA嵌段共聚高分子，並有效地控制其嵌段高分子分子量與分子量分佈，藉由核磁共振儀(NMR)、小角度X光散射儀(Small Angle X-ray Scattering)的分析下，觀察嵌段高分子是否具有微觀相分離行為。

關鍵字

立體規則性高分子 ； 胺化反應

並列摘要

Studies of Conjugated polymers have drawn tremendous research interest 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. This study aims to synthesized novel side-chain conjugated polymers, which have the unique structure of maintaining a syndiospecific stereoregularity in their corresponding poly-1-(4-vinylphenyl)-pyrrole conjugated side-chain. Accordingly, the homopolymer and block copolymers of syndiotactic poly-1-(4-vinylphenyl)-pyrrole were prepared and their corresponding photoluminescence properties were examined and reported. Three synthetic steps were used for the successful syntheses of syndiotactic poly-1-(4-vinylphenyl)-pyrrole:
(Ⅰ)1-(4-vinylphenyl)–pyrrole (monomer) was prepared by coupling 4-bromostyrene with pyrrole via the palladium-catalyst-mediated Buchwald-Hartwig reaction.
(Ⅱ) End-functionalized syndiotactic poly-1-(4-vinylphenylpyrrole) (OH-capped-sP4VPPy) was synthesized by conducting the syndiospecific polymerization of 1-(4-vinylphenyl)-pyrrole in the presence of vinylsialne (chain transfer agent) and syndiospecific metallocene complex catalyst.
(Ⅲ) sP4VPPy-b-PLLA was prepared by conducting the controlled-living ring opening polymerization of L-lactide using the OH-capped-sP4VPPy as the macroinitiator. The resulting stereoregular diblock copolymers were observed to possess precise chemical architectures (define chemical structures with narrow ranges of molecular weight distribution) and hence the study of using these novel block copolymer samples for molecular self-assembly study is currently under way.

並列關鍵字

Buchwald-Hartwig reaction ； stereoregularity

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