研究生: |
王照錡 Chao-Chi Wang |
---|---|
論文名稱: |
以開環歧化聚合反應合成含有降冰片烯基及咔唑基之高分子及其結構與性質之鑑定 Synthesis and Characterization of Polymers Based on Norbornene and Carbazole by Ring-Opening Metathesis Polymerization |
指導教授: |
游進陽
Chin-Yang Yu |
口試委員: |
游進陽
Chin-Yang Yu 王丞浩 Chen-Hao Wang 陳志堅 Jyh-Chien Chen 趙基揚 Chi-Yang Chao 堀江正樹 Masaki Horie |
學位類別: |
博士 Doctor |
系所名稱: |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
論文出版年: | 2019 |
畢業學年度: | 107 |
語文別: | 英文 |
論文頁數: | 177 |
中文關鍵詞: | 開環歧化聚合 、降冰片烯二甲醯亞胺 、環咔唑二烯 、自組裝 、奈米尺寸聚集體 |
外文關鍵詞: | Ring-opening metathesis polymerization, norbornene-based derivatives, carbazolephanediene, self-assembly, nanoaggregates |
相關次數: | 點閱:309 下載:0 |
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開環歧化聚合為一種以釕基引發劑對高環張力單體進行聚合物合成的方式。該方法具有活性聚合的特徵,如合成出來的分子量分布狹窄、低缺陷、可控制末端基和可以控制聚合物分子量的優點,由於引發劑端持續保持反應性,也利於合成共聚聚合物。藉由單體與引發劑的比例變化可以合成出不同分子量和體積比鏈段的共聚聚合物,達到人為改變聚合物的微觀結構以及宏觀性質。
在本研究中,我們利用開環歧化聚合反應對高環張力的單體進行聚合,隨著單體側鏈的不同,如長烷基、三乙二醇基、部分氟烷基,所合成出來的共聚聚合物將具有性質非常不同的兩側鏈段。我們利用含有上述側鏈的降冰片烯二甲醯亞胺及環狀結構咔唑進行開環聚合並得到了各式新式的均聚物及共聚聚合物。本研究之重點為新聚合物之合成及微觀薄膜型態。並對結構導向的共聚聚合物進行形態觀察和光學性質測量,並考量在有機光子晶體或光伏元件中的潛在用途。我們合成了具有不同側鏈的一系列降冰片烯基及咔唑基之新單體和聚合物,並通過核磁共振儀,質譜和凝膠滲透色譜進行結構鑑定。均聚物和共聚聚合物是通過使用第三代格拉布引發劑對單體的開環歧化聚合來獲得。本研究證明了具有不同側鏈的聚合物的自組裝。在降冰片烯基聚合物中,含有氟化鏈的共聚物顯示出了一致的自組裝形態,被認為更容易在聚合物膜中具有自組裝結構。咔唑亞乙基聚合物的帶隙相對較低(2.64至2.79 eV)並且明顯受側鏈影響。由於三乙二醇鏈的高度無序和柔韌性,具有較高組成的三乙二醇取代的咔唑鏈段顯示出球狀奈米尺寸聚集體。
Polymers can be prepared by ring-opening metathesis polymerization (ROMP) of strained monomers, initiated by ruthenium carbene initiator. The resulting polymers exhibited low polydispersities, low defect, controllable end group fashion and the molecular weight of polymers can be tightly controlled by changing the monomer to initiator ratio. In the research proposal, we employ ring-opening metathesis polymerization of highly ring-strained monomers such as alkyl, semi-perfluoroalkyl or triethylene glycol substituted norbornene-based derivatives and carbazolephanediene undergoing ruthenium carbene complexes which can generate a series of well-defined homopolymers and block copolymers. In addition, the molecular weight and the volume ratio of the individual blocks of the polymers can be tailored by the ratio of the monomers employed. Herein, we will use block copolymers and their analogous homopolymers prepared in a predictable manner that exhibits self-assembled nanoscale morphology. The study will focus on polymer synthesis and films generated by spin coating from various solutions and examine the morphology and the optical property based on structure directing block copolymers which may lead to potential use in organic photonic crystals or a photovoltaic device.
The series of new monomers and polymers with different flexible chains have been synthesized and fully characterized by NMR, mass spectroscopy and gel permeation chromatography. The homopolymers and block copolymers can be obtained by the ring-opening metathesis polymerization of their corresponding monomers and comonomers using third generation Grubbs initiator. The self-assembly of polymers with the different side chains have been reported in this research. For norbornene-base polymers, fluorinated chains are thought to be easier to have self-assembled structure in polymer films due to the inimitable aggregation property. The block copolymer contains both fluorinated block and alkyl block shows different size particles with different volume ratio. A series full conjugated polymers were synthesis by carbazolephanediene. The monomers were synthesized by McMurry coupling in few steps. The bandgap of the carbazolevinylene base polymers is relatively low (2.64 to 2.79 eV) and is strongly dependent on the side chains. The carbazolevinylene block copolymers with a higher composition of the triethylene glycol substituted carbazolevinylene block showed sphere-like nanoaggregates due to the highly disorder and flexibility of the triethylene glycol chains. This work demonstrated well control of the polymer microstructures with specific nanoaggregates in solid state.
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