利用鈀金屬觸媒以誘導芳香烴化合物之銜接反應: 合成對位性立體規則性發光材料及其雙嵌段共聚物

Palladium-Catalyst-Mediated Coupling Reactions for the Preparation of Stereoregular Fluorescent Polymers and Diblock Copolymers

陳柏翰(Bo-Han Chen)

指導教授 ： 蔡敬誠

國立中正大學/工學院/化學工程學系/碩士(2015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觸媒)來控制其立體規則性。因此本研究則將注重於開發新型支鏈共軛高分子材料，使高分子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四個方向：
(Ⅰ) 利用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-雙甲基-2-芴基)苯乙烯。
(Ⅱ) 所合成之單體可利用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。
(III) 經由去矽反應及氫硼化-氧化反應可有效得到末端具有氫氧基的高分子( sP(DMFlSty)-OH )。
(Ⅳ) 本研究中還利用Tin觸媒，sP(DMFlSty)-OH做為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sP(DMFlSty)-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 ； Metallocene ； 發光高分子 ； Suzuki 耦合反應 ； 雙嵌段共聚物

並列摘要

Light emitting polymers typically posses the π-conjugated light- emitting units so as to allow the light abortion, 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).
This study aims to synthesized novel side-chain conjugated polymers, which have the unique structure of maintaining a syndiospecific stereoregularity in their corresponding conjugated side-chain.
Our syntheses of these polymers are based on the following synthetic steps:
I.9,9-dimethyl-2-(4-vinylphenyl)-9H-fluorene monomer was synthesized by coupling 4-bromostyrene with aromatic boronic acid through palladium-catalyst-mediated Suzuki cross coupling reaction.
II.End-functionalized vinylsilane -capped-sP(DMFlSty) was synthesized by conducting the syndiospecific polymerization of 9,9-dimethyl-2-(4- vinylphenyl)-9H-fluorene in the presence of dimethylphenylvinylsilane (DMPhVS:chain transfer agent), using Cp*Ti(OMe)3/MAO as the catalyst.
III.The resulting vinylsilane end-capped sP(DMFlSty) was used to undergo the desilylation and hydroboration to generate OH-capped sP(DMFlSty).
IV.sP(DMFlSty)-b-PLLA was prepared by conducting the controlled-living ring opening polymerization of L-lactide using the sP(DMFlSty)–t-OH 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

Stereoregularity ； Light emitting polymers ； Metallocene ； Suzuki reaction ； Diblock Copolymer

參考文獻

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