臺灣博碩士論文加值系統

含偶氮染料(Azobenzene dye)之光致變性高分子在紫外光(λ=365 nm)照射下，會進行反-順異構化反應(trans-cis photoisomerization)，並經由照射其他波長之光源或熱反應進行逆反應；此外，由於此類高分子共聚物兼具有良好的分子排列特性、互溶性及加工性極易驅動的性質可應用於光儲存材料上，因此，相當具有繼續開發研究的潛力及價值。
本研究先合成含有偶氮色團的單體，再加入methyl methacrylate ( MMA )聚合，形成側鏈型高分子共聚物，並探討其光學性質。本研究所合成之共聚物，在Azobenzene上接上拉電子基團(-NO2)，和spacer長度為11 (n=11)的條件下，以不同莫耳比例Azobenzene monomer (偶氮單體) 與MMA的條件進行共聚合反應，所得之共聚物分別以溶液及薄膜兩種條件來探討其光致變，光恢復之現象，希望能借此了解此類高分子共聚物在不同溶液極性影響及實際應用在光儲存材料上的各種現象。

The photochrome of azobenzene dye will induce trans-cis photoisomerization under ultra-visible light﹒The reverse reaction will be reverse by heat or light with different wavelength；Moreover , there are three properties : 1. Good arrangement of polymer , 2. Good solvation , 3. Good process to be drived easily , which can be applied in storage material of light in this kind of copolymer﹒Therefore , it is quite potential and valuable to do further research﹒
This research is to synthesize monomer with azobenzene and copolymerize with methyl methacrylate (MMA)﹒Then the copolymer will become side-chain copolymer﹒The optical property of this copolymer is worthy of research﹒In this study, the azobenzene moiety was attached with the same electron-withdrawing group and the same spacer length(n=11)﹒Further , we synthesize azobenzene and copolymerize with different mole percentage of MMA to induce copolymerizing reaction﹒The copolymer we get after reaction will be discussed individually in the following two situations:1. Solvent polarity；2. Thin film and studied it`s phenomenon of photochrome﹒I would suggest that each kind of phenomenons in the copolymer are affected by different solvent polarity and their application in the storage material of light in practice﹒The study result shows that photochrome wil isomerizes faster with higher mole percentage of azobenzene in the copolymer﹒However, the rate of isomerization will be faster with higher solvent polarity due to more attractions﹒

中文摘要.....................Ⅰ
英文摘要…….................Ⅱ
圖目錄.......................Ⅲ
表目錄……...................Ⅳ
壹、 緒論….…............3
1-1 前言………………………....3
1-2 原理......................4
1-3紫外光/可見光分子吸收光譜法簡介.....................6
1-3-1 溶液方面.........................................6
1-3-2 比耳定律的限制................................8
1-4溶劑的效應(solvent effect) .........................9
1-4 -1靜電的影響…..................................9
1-5光化學之發色原理...................................13
1-6光化學/光儲存機制..................................13
1-7文獻回顧...........................................15
貳、 實驗.............................................17
2-1實驗藥品...........................................17
2-2實儀儀器...........................................18
2-3合成步驟...........................................19
2-4共聚物合成流程圖...................................22
2-5光致變性、光恢復性測試步驟.........................23
2-5-1溶液中之光致變性、光恢復性測試...................23
2-5-2 薄膜中之光致變性、光恢復性測試..................24
參、 結果與討論.......................................25
3-1共聚物之合成鑑定...................................25
3-2光致變性質部份.....................................27
3-2-1不同比例共聚物之光致變與光恢復現象(溶液部份).....27
3-2-2不同極性溶劑對共聚物光致變與光恢復之影響.........27
3-2-3共聚物薄膜光致變、光恢復部份.....................30
肆、 結論.............................................93
伍、 參考文獻.........................................94
圖目錄
fig. 1-1：偶氮分子之順式-反式結構轉換圖................5
fig. 1-2：反射及散射示意圖.............................7
fig. 1-3：由富朗-康頓原理來描述當中四種能階之關係圖....10
fig. 1-4 : 由基態和激發態在溶劑中所造成之紅位移和藍位移...11
fig. 1-5 : 溶劑介電鬆弛(solvent dielectric relaxation )的吸收和能階圖…........................... ...................12
fig. 1-6 : 光儲存機制圖.................................14
fig. 3-1 : Poly(M11NO2-co-MMA)-(0.1:99.9)之NMR圖……….....40
fig. 3-2：Poly(M11NO2-co-MMA)-(1:99)之NMR圖…………………41
fig. 3-3：Poly(M11NO2-co-MMA)-(10:90)之NMR圖………………..42
fig. 3-4：Poly(M11NO2-co-MMA)-(30:70)之NMR圖………………..43
fig. 3-5：Poly(M11NO2-co-MMA)-(50:50)之NMR圖………………..44
fig. 3-6：Poly(M11NO2-co-MMA)-(70:30)之NMR圖………………..45
fig. 3-7：Poly(M11NO2-co-MMA)-(100%)之NMR圖………………..46
fig. 3-8：Poly(M11NO2-co-MMA)-(0.1：99.9 )在15℃THF溶液中之光致變圖…...................................................47
fig. 3-9：Poly(M11NO2-co-MMA)-(0.1：99.9 )在15℃THF溶液中之光恢復圖…....................................................48
fig. 3-10：Poly(M11NO2-co-MMA)-(0.1：99.9 )在21℃ CHCL33溶液中之光致變圖.......................................................49
fig. 3-11：Poly(M11NO2-co-MMA)-(0.1：99.9 )在21℃ CHCL3溶液中之光恢復圖..................................................50
fig. 3-12：Poly(M11NO2-co-MMA)-(0.1：99.9 )在24℃ DMF溶液中之光致變圖........................................................51
fig. 3-13：Poly(M11NO2-co-MMA)-(0.1：99.9 )在DMF溶液中之光恢復圖................................................52
fig. 3-14：Poly(M11NO2-co-MMA)-(1：99 )在13℃ THF溶液中之光致變圖....................................................53
fig .3-15：P-11-NO2-1%在24℃DMF溶液中之光恢復圖…………..54
fig .3-16：Poly(M11NO2-co-MMA)-(1：99 )在15℃ THF溶液中之光致變圖...........................................................55
fig. 3-17：Poly(M11NO2-co-MMA)-(1：99 )在15℃ THF溶液中之光恢復圖.................................................. ......56
fig. 3-18：Poly(M11NO2-co-MMA)-(1：99 )在25℃ NMP溶液中之光致變圖.........................................................57
fig. 3-19：Poly(M11NO2-co-MMA)-(1：99 )在25℃ NMP溶液中之光恢復圖.................................................. .......58
fig. 3-20：Poly(M11NO2-co-MMA)-(50：50 )在 13℃ THF溶液之光致圖.............................................. ...........59
fig. 3-21：Poly(M11NO2-co-MMA)-(50：50 )13℃ THF溶液之光恢復圖............................. ............................60
fig. 3-22：Poly(M11NO2-co-MMA)-(50：50 )在THF溶液之光致變圖……………………………………………………………..61
fig. 3-23：Poly(M11NO2-co-MMA)-(50：50 )在THF溶液之光恢復圖……………………………………………………………..62
fig. 3-24：Poly(M11NO2-co-MMA)-(50：50 )在18℃ CH3 CN溶液之光致變圖………………………………………………………..63
fig. 3-25：Poly(M11NO2-co-MMA)-(50：50 )在18℃ CH3 CN溶液之光恢復圖………………………………………………………..64
fig.3-26：Poly(M11NO2-co-MMA)-(50：50 )在13℃ THF溶液之光致變圖…………………………………………………………..65
fig.3-27： Poly(M11NO2-co-MMA)-(50：50 ) 18℃ CH3CN溶液中之光恢復圖………………………………………………………..66
fig.3-28：Poly(M11NO2-co-MMA)-100% 在13℃ THF溶液之光致變圖……………………………………………………………..67
fig.3-29：P-11-NO2-100% 在13℃在THF溶液之光恢復圖………..68
fig. 3-30：P-11-NO2-100% 在13.5℃ 在C6H5CH3溶液之光致變圖…69
f ig. 3-31：P-11-NO2-100% 在13.5℃ 在C6H5CH3溶液之光恢復圖.70
fig. 3-32：P-11-NO2-100% 在22℃ 在CH3CL溶液之光致變圖……71
fig. 3-33：P-11-NO2-100% 在22℃ 在CH3CL溶液之光恢復圖……72
f ig.3-34：P-11-NO2-100% 在25℃在 NMP溶液之光致變圖………73
fig. 3-35：P-11-NO2-100% 在25℃ 在NMP溶液之光恢復圖………74
Fig.3-36：P0ly(M11NO2-co-MMA)-(1：99)-薄膜光致變圖………….75
Fig.3-37：P0ly(M11NO2-co-MMA)-(1：99)-薄膜光恢復圖………….76
Fig.3-38：P0ly(M11NO2-co-MMA)-(10：90)-薄膜光致變圖…………77
Fig.3-39：P0ly(M11NO2-co-MMA)-(10：90)-薄膜光恢復圖…………78
Fig.3-40：P0ly(M11NO2-co-MMA)-(30：70)-薄膜光致變圖…………79
Fig.3-41：P0ly(M11NO2-co-MMA)-(30：70)-薄膜光恢復圖…………80
Fig.3-42：P0ly(M11NO2-co-MMA)-(50：50)-薄膜光致變圖…………81
Fig.3-43：P0ly(M11NO2-co-MMA)-(50：50)-薄膜光致變圖…………82
Fig.3-44：P0ly(M11NO2-co-MMA)-(70：30)-薄膜光致變圖…………..83
Fig.3-45：P0ly(M11NO2-co-MMA)-(70：30)-薄膜光恢復圖…………84
Fig.3-46：P0ly(M11NO2-co-MMA)-100%-薄膜光致變圖…………….85
Fig.3-46：P0ly(M11NO2-co-MMA)-100%-薄膜光致變圖……………86
fig. 3-48：Poly(M11NO2-co-MMA)-(1：99)之分子量分布圖………..87
fig.3-49：Poly(M11NO2-co-MMA)-(10：90)之分子量分布圖…………88
fig. 3-50： Poly(M11NO2-co-MMA)-(30：70)之 分子量分布圖…..89
fig.3-51： Poly(M11NO2-co-MMA)-(50：50)之 分子量分布圖..……90
fig.3-52：Poly(M11NO2-co-MMA)-(70：30)之GPC分子量分布圖……91
fig.3-53：P-11-NO2-100%之GPC分子量分布圖…………..…………..92
表目錄
Table 3-1………………………………………………………………33
Table 3-2………………………………………………………………34
Table 3-3………………………………………………………………35
Table 3-4………………………………………………………………36
Table 3-5………………………………………………………………37
Table 3-6………………………………………………………………38
Table 3-7………………………………………………………………39

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