利用鈀金屬觸媒以誘導芳香烴化合物之銜接反應: 合成含對位發光基團之對位聚苯乙烯 新型立體規則性發光聚合物

Palladium-Catalyst-Mediated Coupling Reactions for the Preparation of Light-Emitting Units Containing Syndiotactic Polymers of Styrene Derivatives

劉佩姍(Pei-Shan Liou)

指導教授 ： 蔡敬誠

國立中正大學/工學院/化學工程學系/碩士(2014年)

摘要

一般發光聚合物材料皆具備共軛(如芳香苯環結構)之發光結構單元，但因受限於高分子合成方法，具備發光單元之聚合物尚未被探討立體規則性結構對發光特性產生之影響，苯乙烯單體在聚合時可應用配位聚合反應觸媒(如Metallocene, Zieglar-Natta)來控制其立體規則性。由於苯乙烯單體具備芳香苯環結構，在單體或高分子設計上如能有效將苯乙烯之苯環共軛結構銜接上其它共軛結構單元，則可形成具備發光特性之苯乙烯衍生物，合成新型之立體規則性發光聚合物(stereoregular polymers with light-emitting structural units)，為了完成我們針對發光新材料的開發，本研究的內容則包含下列兩部份：

Part1
(Ⅰ) 利用Metallocene (Cp*Ti(OMe)3/MAO)觸媒系統聚合4-溴苯乙烯(4BrS)單體，以合成具有對位性之聚4-溴苯乙烯(sP4BrS) 立體規則高分子，並在反應過程中藉由加入二甲基苯基乙烯基矽烷(dimethylphenylvinylsilane)作為鏈轉移劑，以控制高分子分子量分佈，再利用去矽基反應、氫硼化－氧化反應，合成出高分子末端帶有氫氧基之聚合物 ( OH-capped sP4BrS )，做為合成嵌段共聚物的關鍵起始物。
(Ⅱ) 使用鈀金屬觸媒Pd(PPh3)4，誘導sP4BrS進行Suzuki 耦合反應，改質苯對位位置帶有halides(-Br)側鏈基之化學結構，以合成苯對位位置具有多苯取代基之對位苯乙烯衍生物之立體規則聚合物，且末端具備特殊官能基。

Part2
(Ⅰ) 將苯對位位置帶有halides側鏈基的4-溴苯乙烯單體，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9,9-diethyl-2-(4-vinylphenyl)-9H-fluorene，此一結構經實驗證實具備photoluminescence效應。
(Ⅱ) 使用Metallocene (Cp*Ti(OMe)3/MAO)觸媒系統聚合此側鏈帶有光電基團的苯乙烯衍生單體9,9-diethyl-2-(4-vinylphenyl)-9H- fluorene，並在Cp*Ti(OMe)3/MAO觸媒系統下以DMPVS做為鏈轉移劑，合成出末端帶有乙烯基矽烷官能基之聚合物(DMPVS-capped Syndiotactic poly[9,9-diethyl-2-(4-vinylphenyl)-9H- fluorene] )。

關鍵字

金屬茂觸媒 ； 立體規則性發光高分子 ； Suzuki耦合反應

並列摘要

Light emitting polymers typically posses the -conjugated light- emitting units so as to allow the light aborption, energy transfer and light-emitting processes to take place. Currently, stereoregularity effects of light-emitting polymers have not been fully investigated because of the difficulty in the syntheses of stereoregular light-emitting polymers.
The stereorularity of styrene monomer can be controlled by stereospecific polymerization of styrene using stereoregular coordination complexes as the polymerization catalysts (e.g., Zieglar-Natta and metallocene). As the styrene monomer has a benzene ring, strucural modification of the -conjugated system by connecting other -conjugated structures on to the benzene ring of styrene can lead to the formation of a styrene derivative which is able to show light-emitting characteristic. Subsequently, stereospecific polymerization of the light-emitting stryene derivative monomer (vinylarene) provides the fesible synthetic route for the syntheses of stereoregular light-emitting polymers.
Our syntheses of these unique vinylarene -based polymers are based on the following synthetic steps:

Part1
(Ⅰ) End-functionalized syndiotactic poly-4- bromostyrene (vinylsilane
-capped-sP4BrS) was synthesized by conducting the syndiospecific polymerization of 4-bromostyrene in the presence of dimethylphenylvinylsilane (DMPhVS:chain transfer agent), using Cp*Ti(OMe)3/MAO as the catalyst.
(Ⅱ) Syndiotactic poly-4-bromostyrene (sP4BrS) can be used to undergo the palladium-catalyst-mediated Suzuki coupling reaction for the generation of syndiotactic vinlyarene which process additional aromatic structures at the para-position of styrene.

Part2
(Ⅰ)9,9-diethyl-2-(4-vinylphenyl)-9H-fluorene monomer was synthesized by coupling 4-bromostyrene with aromatic boronic acid through palladium-catalyst-mediated Suzuki cross coupling reaction. The resulting 9,9-diethyl-2-(4-vinylphenyl)-9H-fluorene monomer exhibits light-emitting property as demonstrated by PL analyses.

(Ⅱ) DMPhVS-capped Syndiotactic poly[9,9-diethyl-2-(4-vinylphenyl) -9H-fluorene] was synthesized by conducting the syndiospecific polymerization of 9,9-diethyl-2-(4-vinyl phenyl)-9H-fluorene in the presence of dimethylphenylvinylsilane (DMPhVS:chain transfer agent), using Cp*Ti(OMe)3/MAO as the catalyst.

並列關鍵字

Suzuki coupling reaction ； Stereoregularity ； Metallocene

參考文獻

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