以開環歧化聚合合成聚亞芬香基乙烯之共軛嵌段共聚物

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研究生：	蔣欣妤 Chiang, Hsin Yu
論文名稱：	以開環歧化聚合合成聚亞芬香基乙烯之共軛嵌段共聚物 Conjugated Block Copolymers of Poly(arylenevinylene)s by Ring-Opening Metathesis Polymerization
指導教授：	堀江正樹 Horie, Masaki
口試委員:	游進陽 Yu, Chin Yang 蘇安仲 Su, An Chung
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2016
畢業學年度：	104
語文別：	英文
論文頁數：	85
中文關鍵詞：	開環歧化聚合反應、予體受體共軛嵌段聚合物、聚亞芳香基乙烯
外文關鍵詞：	Ring-opening metathesis polymerization, donor-accptor conjugated block copolymer, poly(arylenevinylene)s
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我們利用Mcmurry偶聯反應合成由電子予體CPDT、BTh，電子受體DTBT組成之具有高度環張力之分子，做為單體，並藉由氫-1、碳-13核磁共振儀以及快速原子轟擊(FAB)質譜儀確認其單體結構。接著，透過Grubbs催化劑引發開環歧化聚合反應(Ring-opening metathesis polymerization, ROMP)，合成出一系列具亞芬香基乙烯衍生物，具有低PDI，低缺陷的特性，且可藉由單體與催化劑的比例來控制其分子量。除此之外，在共嵌段聚合物的合成反應中，我們利用相似的實驗手法，先將第一段之單體利用ROMP使其開環聚合後，緊接著加入第二段之單體，同樣地在ROMP下開環聚合成功合成出予體-受體共軛共嵌段聚合物(donor-acceptor) PDTBT-b-PCPDT、PDTBT-b-PBTh，以及予體-予體共軛共嵌段聚合物(donor-donor) PDTh-b-PCPDT。
我們探討了所有高分子的光學、電化學、形態學的性質。共嵌段聚合物具有許多獨特的性質，例如，較寬的紫外光/可見光吸收光譜，較窄的能帶隙(bandgap)，及相分離，是十分具有發展潛力之太陽能電池材料。

In this work, a series of the novel poly(arlyenevinylene)s has been prepared by ring-opening metathesis polymerization (ROMP) of strained cyclic vinylene monomers composed of conjugated units such as cyclopentadithiophene (CPDT), bis(thienyl)-benzothiadiazole (DTBT), and bis(hexyl)-bithiophene (BTh), which were initiated by ruthenium-based catalysts. The monomers were synthesized by McMurry coupling using TiCl4/Zn and the products were characterized by 1H and 13C NMR spectroscopy and fast atom bombardment (FAB) mass spectrometry. In ROMP, molecular weight of the polymers can be varied by changing the monomer to catalyst ratio. Furthermore, the resulting polymers have less structural defects. Diblock copolymers of poly(arylenevinylene)s were also synthesized by similar procedure, in which first-block was synthesized by ROMP of DTBT monomer, followed by subsequent addition of the second and third monomers of CPDT and BTh.
The block copolymers exhibit multiple functions derived from each block, e.g. wider-range UV-vis absorption and higher and lower HOMO-LUMO levels than those of homopolymers. In addition, morphology of homopolymers and block copolymers were studied by atomic force microscopy (AFM) to observe microphase separation in their film state. These type of polymers are potentially useful as efficient light-harvesting materials in OPV devices.

中文摘要    ......4
Abstract......5
Chapter 1. Introduction and purpose......8
1 Introduction to conjugated polymers......8
1.1 Conjugated polymers......8
1.2 Organic photovoltaics based on conjugated polymers......8
1.4 Poly(phenylenevinylene)s......13
2 Ring-opening metathesis polymerization......14
2.1 Olefin metathesis......14
2.2 Mechanism of ROMP......14
2.3 Catalysts for living ROMP......16
2.4 Poly(arylenevinylene) from living ROMP......18
3 Microphase separation of block copolymers......19
3.1 Self-assembly of block copolymers......20
3.2 A donor-acceptor conjugated block copolymer of poly(arylenevinylene)s through ROMP    22
3.3 Phase behaviors in rod-coil block copolymers......24
3.4 Phase behaviors in rod-rod block copolymers......25
4 Aim of this project......26
Chapter 2 Synthesis and Characterization of polymers......28
1 Synthesis of monomers......28
2 Synthesis of catalyst......33
2.1 Comparison of the reactivity of the 2nd and 3rd Grubbs catalysts......35
3 Synthesis of polymers......36
3.1 Synthesis of homopolymers......37
3.1.1 Comparison of the reactivity of M3a and M3b......8
3.2 Synthesis of block copolymers......40
3.2.1 Synthesis of rod-rod block copolymer D2......40
3.2.2 Synthesis of rod-rod block copolymer D3......42
3.2.3 Synthesis of rod-coil block copolymer D4......44
3 Properties of homopolymers and block copolymers......46
3.1 Optical properties......46
3.2 Electrochemical properties......50
3.3 Thermal properties......53
3.4 Morphology......55
Chapter 3 Conclusions......59
Chapter 4 Experimental section......61
1 General methods......61
2 Synthesis of monomers......61
2.1 Synthesis of bis(ethylhexyl)-bithiophene (BTh) (M3)......61
2.1.1 Synthesis of 3-Hexylthiophene (1)......61
2.1.2 Synthesis of bromohexylthiophene (2)......62
2.1.3 Synthesis of 3,3’-dihexyl-2,2’-bithiophene (3)......62
2.1.4 Synthesis of 3-3’-dihexyl-[2-2’-bithiophene]-5,5’- dicarbaldehyde (4)......63
2.1.5 Synthesis of 3-3’-bis(hexyl) 2,2’-bithiophene M3a and M3b......64
3 Synthesis of 3rd generation Grubbs catalyst......65
4 Synthesis of polymers......66
4.1 Synthesis of H3......66
4.2 Synthesis of D2a......66
4.2 Synthesis of D2b......67
4.3 Synthesis of D2c......68
4.4 Synthesis of D3......69
4.5 Synthesis of D4a......70
References......84


 

                                

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