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研究生(中)楊凱能
研究生(英)kai-neng Yang
論文名稱(中)偶氮系梳狀側鏈液晶高分子的光變色性與介電行為研究
論文名稱(英)Dielectric and Photochromic Behavior in Comb-Shaped Liquid Crystalline Polymers Containing Azobenzene Side Group
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指導教授(中)李選能
指導教授(英)Sung-Nung Lee
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學位類別碩士
畢業學年度88
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語文別中文
關鍵字(中)光致變 介電 梳狀型高分子 梳狀型液晶高分子
關鍵字(英)Photochromic Behavior SCLCP Comb-Shaped Liquid Crystalline Polymer Dielectric Behavior Comb-Shaped Polymer
摘要(中)摘 要 將偶氮色團(Azobenzene dye)接於具液晶特性之側鏈液晶高分子上,由於具有良好的分子排列特性、互溶性、加工性及易驅動性等性質,適用作光資訊儲存材料,近年日益引起重視。本研究合成六種含偶氮基團之梳狀型側鏈液晶高分子,偶氮基團之對位上接有具不同拉電子強度之取代基(-NO2、-CN、-COCH3) ,而液晶軟鏈部份則分別為(-CH2-)3及(-CH2-)9。 所合成之六種梳狀液晶高分子其結構均經過NMR、IR、GPC、UV之分析鑑定確定。熱重分析儀(TGA)測試,在250℃時仍具良好的熱穩定性。DSC圖譜顯示,大部份高分子在加熱過程中形成特殊的中間相(POM顯示接近Smectic相)。此含偶氮色團梳狀液晶高分子在光照射下(λ=365 nm),產生順-反式異構化反應(trans-cis photoisomerzation),並有光及熱可恢復之特性。其軟鏈(Spacer)越長、苯環上拉電子基越強,此恢復愈快,在介電鬆弛研究中,亦發現Spacer長度與拉電子基的強弱也會影響到β-鬆弛發生的位置。其中含-NO2基之β-鬆弛發生溫度最低。另外各種高分子之Tm點及Tg點亦可經發生由δ-鬆弛及α-鬆弛的位置上,更精確獲的測得。
摘要(英)Abstract Photochromic dye molecules (Such as azobenzenes) change their molecular shape upon photo irradiation, and this property has been used extensively to control the orientation of liquid crystals by light. Besides, azobenzene liquid crystals have been developed, in which the azobenzene moiety plays roles as both mesogens and photosensitive chromophores. The trans form of azobenzene derivative is rod-like, which stabilizes the LC phase, whereas the cis form is bent and destabilizes the LC phase when it is present. Therefore, the trans-cis photoisomerization of azobenzene in the LC phase can cause disorganization of the phase structure. In addition, the cis-trans back-isomerization can take place either by a thermal process or a photochemical process. All these properties enable the comb-shaped side-chain LC polymer (SCLCP) containing an azobenzene moiety a promising material for optical switch and image storage. This study synthesized six SCLCPs of this type in which the azobenzene moiety was attached with different electron-withdrawing group (i.e.,-NO2,-CN,-COCH3) on the para position, and the soft spacer used was either (-CH2-)3 or (-CH2-)9 segment. All their structure were characterized by GPC, NMR, IR, UV, DSC, TGA and POM. All there SCLCPs were stable up to 250℃, and exhibited some stable mesophases (mostly Smectic phase), as confirmed by POM and DSC observations. Photoirradiation was performed with a 100W high-pressure Hg lamp. The change in transmittance of 365 nm absorbance band (corresponding to π-π* transition of trans-azobenzene) was monitored as a function of irradiation time. These results showed that the spacer length and electron-withdrawing capability were the two factors which enhancing the backward isomerization processes, but not for the forward trans-cis isomerization process, Dielectric relaxation studies exhibited a more clear-cut picture for the mesophase transitions of these SCLCP than that of DSC and POM showed. The two factors mentioned above also affects the location of occurrence of β-relaxation.
論文目次目 錄 一、 緒論…………………………………………………………..1 1-1 前言……………………………………………………..1 1-2液晶簡介…………………………………………………3 1-3光致變系統簡介…………………………………………5 1-4介電性質簡介……………………………………………10 1-5文獻回顧…………………………………………………14 二、 原理…………………………………………………………..17 2-1光致變光學基本原理……………………………………17 2-2介電原理…………………………………………………23 2-2-1電介質之巨觀特性……………………………….23 2-2-2極化現象………………………………………….26 2-2-3介電損失及複介電常數………………………….27 2-2-4介電鬆弛…………………………………….……31 2-3光儲存原理………………………………………………36 三、 實驗…………………………………………………………..37 3-1實驗藥品…………………………………………………37 3-2實驗儀器…………………………………………………38 3-3實驗步驟與方法…………………………………………39 3-3-1高分子合成流程圖……………………………….39 3-3-2 合成步驟…………………………………………41 3-4光致變測試方法…………………………………………44 3-5介電性質之量測方法……………………………………45 四、 結果與討論…………………………………………………..46 4-1高分子的結構鑑定………………………………………46 4-2熱分析與液晶性探討……………………………………52 4-3光致變性…………………………………………………54 4-4介電行為…………………………………………………56 五、 結論…………………………………………………………..121 參考文獻………………………………………………………….123 表 目 錄 Table 1 ‘H(DMSO、Chroform-d,ppm)光譜………….……46 Table 2 FT-IR吸收光譜 …………………………………….….50 Table 3 UV吸收光譜……………………………………………51 Table 4 六種高分子分子量表…………………………………..51 Table 5 高分子相變化……………………………………….….53 圖 目 錄 Figure 1.1 CD-RW讀寫原理……………………………………..3 Figure 1.2 Polarization mechanism of a dielectric material……….12 Figure 1.3側鏈液晶高分子之介電鬆弛…………………………13 Figure 2.1光變色染料之能階轉換圖……………………………20 Figure 2.2光變色機構行為模式圖………………………………22 Figure 2.3 Structure of simple capacitor:(a)the dielectric is a vacuum, and(b)the dielectric is more polarizable than a vacuum…………………………………………25 Figure 2.4 The polarization effect of free charges and bound charges…………………………………………………25 Figure 2.5 The chart of different polarizations versus frequencies…………………………………………….27 Figure 2.6 The parallel model of RC circuit………………………29 Figure 2.7 The relationship diagram of I1 and Ic………………….29 Figure 2.8 The diagram with fitting Debye equation of dielectric properties versus frequencies……………….33 Figure 2.9 Cole-Cole plots of the dielectric relaxation……………35 Figure 2.10 光儲存機制………………………………………….36 Figure 4-1梳狀液晶高分子結構…………………………………57 Figure 4-2 AzoNO2之NMR圖……………………………………58 Figure 4-3 AzoCN之NMR圖……………………………………59 Figure 4-4 AzoAc之NMR圖…………………………………….60 Figure 4-5 S3NO2之NMR圖…………………………………….61 Figure 4-6 S3CN之NMR圖……………………………………..62 Figure 4-7 S3Ac之NMR圖………………………………………63 Figure 4-8 S11NO2之NMR圖……………………………………64 Figure 4-9 S11CN之NMR圖…………………………………….65 Figure 4-10 S11Ac之NMR圖……………………………………66 Figure 4-11 M3NO2之NMR圖…………………………………..67 Figure 4-12 M3CN之NMR圖……………………………………68 Figure 4-13 M3Ac之NMR圖……………………………………69 Figure 4-14 M11NO2之NMR圖…………………………………70 Figure 4-15 M11CN之NMR圖………………………………….71 Figure 4-16 M11Ac之NMR圖………………………………….72 Figure 4-17 PM3NO2之NMR圖…………………………………73 Figure 4-18 PM3CN之NMR圖…………………………………74 Figure 4-19 PM3Ac之NMR圖…………………………………75 Figure 4-20 PM11NO2之NMR圖……………………………….76 Figure 4-21 PM11CN之NMR圖………………………………..77 Figure 4-22 PM11Ac之NMR圖…………………………………78 Figure 4-23 PM3NO2之FT-IR 圖譜……………………………..79 Figure 4-24 PM3CN之FT-IR圖譜………………………………80 Figure 4-25 PM3Ac之FT-IR 圖譜………………………………81 Figure 4-26 PM11NO2之FT-IR圖譜……………………………82 Figure 4-27 PM11CN之FT-IR圖譜…………………………….83 Figure 4-28 PM11Ac之FT-IR圖譜……………………………..84 Figure 4-29 PM3NO2(UV spectroscopy)……………………..85 Figure 4-30 PM11NO2(UV spectroscopy)…………………….85 Figure 4-31 PM3CN(UV spectroscopy)………………………86 Figure 4-32 PM11CN(UV spectroscopy)……………………..86 Figure 4-33 PM11Ac(UV spectroscopy)………………………87 Figure 4-34 PM11Ac(UV spectroscopy)………………………87 Figure 4-35 PM3NO2之MW Distribution圖譜………………….88 Figure 4-36 PM11NO2之MW Distribution圖譜…………………88 Figure 4-37 PM3CN之MW Distribution圖譜…………………..89 Figure 4-38 PM11CN之MW Distribution圖譜…………………89 Figure 4-39 PM3Ac之MW Distribution圖譜…………………..90 Figure 4-40 PM11Ac之MW Distribution圖譜………………….90 Figure 4-41 熱重量分析(TGA)圖譜………………………….91 Figure 4-42 S3CN之DSC圖譜………………………………….92 Figure 4-43 S3Ac之DSC圖譜…………………………………..93 Figure 4-44 S11NO2 之DSC圖譜……………………………….94 Figure 4-45 M11NO2 之DSC圖譜………………………………95 Figure 4-46 S3Ac 之POM圖(145℃,Heating,200×)……..96 Figure 4-47 S3Ac 之POM圖(175℃,Heating,200×)……..96 Figure 4-48 S3Ac 之POM圖(120℃,cooling,400×)……..97 Figure 4-49 S3Ac 之POM圖(75℃,Heating,200×)………97 Figure 4-50 S3CN 之POM圖(135℃,Heating,200×)…….98 Figure 4-51 S11Ac 之POM圖(105℃,Heating,200×)……98 Figure 4-52 S11CN 之POM圖(105℃,Heating,200×)…...99 Figure 4-53 S11NO2 之POM圖(105℃,Heating,400×)…..99 Figure 4-54 PM3NO2 之DSC圖譜………………………………100 Figure 4-55 PM3CN 之DSC圖譜……………………………….101 Figure 4-56 PM3Ac 之DSC圖譜………………………………..102 Figure 4-57 PM11NO2 之DSC圖譜……………………………..103 Figure 4-58 PM11CN 之DSC圖譜………………………………104 Figure 4-59 PM11Ac之DSC圖譜………………………………..105 Figure 4-60 PM3NO2之POM圖(110℃,400×)……………..106 Figure 4-61 PM3CN之POM圖(120℃,200×)……………...106 Figure 4-62 PM3Ac之POM圖(180℃,400×)………………107 Figure 4-63 PM11NO2之POM圖(90℃,400×)……………..107 Figure 4-64 PM11CN之POM圖(70℃,400×)………………108 Figure 4-65 PM11Ac之POM圖(85℃,400×)……………….108 Figure 4-66 PM3NO2光致變性(29℃)…………………………109 Figure 4-67 PM3NO2光恢復性(29℃)…………………………109 Figure 4-68 PM11NO2光致變性(29℃)………………………..110 Figure 4-69 PM11NO2光恢復性(29℃)………………………..110 Figure 4-70 PM3CN光致變性(29℃)………………………….111 Figure 4-71 PM3CN光恢復性(29℃)………………………….111 Figure 4-72 PM11CN光致變性(29℃)…………………………112 Figure 4-73 PM11CN光恢復性(29℃)…………………………112 Figure 4-74 PM3Ac光致變性(29℃)…………………………..113 Figure 4-75 PM3Ac光恢復性(29℃)…………………………..113 Figure 4-76 PM11Ac光致變性(29℃)…………………………114 Figure 4-77 PM11Ac光恢復性(29℃)…………………………115 Figure 4-78 PM3NO2放光圖譜……………………………………116 Figure 4-79 PM3NO2光致變性(22℃)…………………………116 Figure 4-80 PM3NO2光恢復性(22℃)…………………………117 Figure 4-81 PM11NO2光致變性(22℃)………………………..117 Figure 4-82 PM11NO2光恢復性(22℃)………………………..118 Figure 4-83 PM3NO2 之介電鬆弛圖……………………………..118 Figure 4-84 PM3CN之介電鬆弛圖……………………………….119 Figure 4-85 PM3Ac之介電鬆弛圖…………………………….…119 Figure 4-86 PM11NO2之介電鬆弛圖………………………….…120 Figure 4-87 PM11CN之介電鬆弛圖……………………………..120 Figure 4-88 PM11Ac之介電鬆弛圖……………………………...121 Figure 4-89 dielectric relaxation at 10KHz………………..…..121
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