由於超分枝狀聚合物為具有高度支化的球形大分子，其不規則分枝間含有大量內部空隙，可以減少分子間接觸所產生的作用力，進而減少聚集或激發雙體的生成，並且有良好的溶解度。而聚喹啉雜環高分子則具有良好的熱及氧化度。超分枝狀聚合物和聚喹啉由於上述性質經常應用於發光二極體上，故本研究將聚喹啉導入樹枝狀結構，合成可應用於發光二極體上的發光層高分子。
本研究主要合成出四種分歧度由低至高(HB-1至HB-4)的分枝狀聚合物，並探討其發光性質、熱性質、電化學性質與元件效能的差異。超分枝狀聚合物為全芳香環喹啉剛硬結構，具良好熱性質，主要熱裂解溫度高達571 ℃以上，Tg至少在245 ℃以上，結果顯示分歧度越高的聚合物其熱穩定性越好。四種聚合物在液態及固態的UV及PL光譜皆相似，固、液體皆有極高的量子效率(其量子效率介於0.68 ~0.74間)，而光致光及電致光光譜強度也不會因加熱(至200 ℃以上)而降低，因此具有良好的熱及光譜穩定性。

The highly branched hyperbranched polymers (HBPs) possess large inner space among the irregular branches and the inter-chain contacts inside the globular HBPs can be greatly inhibited. With the unique structural features, HBPs have good solubility in common organic solvent and reduced possibility to form excimer and aggregated species. On the other hand, the wholly aromatic polyquinolines are reported to have excellent thermal and oxidative stability. With the above superior properties, HBPs and polyquinolines are commonly used as emitting materials in light-emitting diodes (LEDs). Therefore, quinioline moiety was implanted into HBPS in this study to prepare materials with superior properties to be used in LED pplications.
Four polyquinoline HBPs with different branching densities (designated as HBP-1 to -4 from low to high densities) were prepared and their optical, thermal, electrochemical properties and device performance were measured and analyzed. The rigid, wholly heterocyclic polyquinolines HBPs have excellent thermal stability with a high Tg (> 245 ℃) and high decomposition temperature starting at 571 ℃. The solution and the solid samples have similar UV-vis absorption and PL emission spectra. The resultant samples have high quantum efficiencies with the measured values ranged from 0.68 to 0.74. Most importantly, thermal annealing at high temperatures (> 200 ℃) resulted in no changes on the corresponding photoluminescent and electroluminescent emission spectra, which indicates the high thermal and spectral stabilities of all HBP polyquinolines in this study.

論文審定書...................................………………….……………………………….... i
誌謝...................................………………….……………………………….............. ii
中文摘要...........................................………………….…………………………… iii
英文摘要....…………………………………………………………………............. iv
圖目錄.........……………………………………………………....................……. viii
表目錄.....................................………………………………..…………………… xi
附錄圖.................................……………………………….....…………………… xiii
第一章 前言.........................………………………………………………………… 1
1-1 超分枝狀聚合物之發展背景…...........….....................………………... 1
1-2 超分枝狀聚合物與樹枝狀聚合物之比較….........................…………… 3
1-3 超分枝狀聚合物之常見合成方式……......................…………………... 4
1-4 超分枝狀聚合物之特性……..............................………………………... 8
1-5 超分枝狀聚合物之應用…...................……........……………………... 9
1-6 回顧發光聚合物之超分枝狀結構……………..……………………...... 10
1-6.1 減少分子間作用力(聚集或激發雙體)……............……………...... 10
1-6.2 提高熱與光學穩定性…...................……........……………………... 12
1-7 聚喹啉之介紹……..............................…………..…………………........ 12
1-8 研究動機……......................................…………..………………..…...... 15
第二章 實驗部分..................................……………………………... 16
2-1 實驗藥品…………………........................………………………............ 16
2-2 儀器分析…..........................……………………………………................ 16
2-3 合成方式………………......................……………………………............ 17
2-3.1 合成tris(4-nitrophenyl)amine (TPA-NO2)……....................................... 17
2-3.2 合成tris(3-phenylbenzo[c]isoxazol-5-yl)amine (TPA-Bz)...................... 17
2-3.3 合成(5,5',5'-nitrilotris(2-aminobenzene-5,1-diyl))tris(phenylmethanone)
(TPA-Pm)………...................................................................................... 18
2-3.4 合成2,3,4,5-tetraphenylthiophene (TP).................................................... 19
2-3.5 合成2,5-bis(4-nitrophenyl)-3,4-diphenylthiophene (TP-NO2)................ 20
2-3.6 合成3-phenyl-5-(3,4-diphenyl-5-(3-phenylbenzo[c]isoxazol-5-yl)
thiophen-2-yl)benzo[c]isoxazole (TP-Bz)............................................... 21
2-3.7 合成5,5'-(3,4-diphenylthiophene-2,5-didiyl)bis(2-amino-5,1-phenylene))
bis(phenylmethanone) (TP-Pm)............................................................... 22
2-3.8 合成超分枝狀聚合物之模型化合物....................................................... 22
2-3.9 合成超分枝狀聚合物(HB)...................................................................... 24
第三章 結果與討論................................................................................................. 28
3-1 合成與鑑定.................................................................................................. 28
3-2 模型化合物之熱與光電性質分析.............................................................. 30
3-2.1 TGA分析.................................................................................................. 30
3-2.2 UV與PL分析............................................................................................ 31
3-2.3 PL分析...................................................................................................... 32
3-2.4 相對量子效率........................................................................................ 35
3-2.5 CV分析...................................................................................................... 35
3-3 超分枝狀聚合物之分子量分析.................................................................. 37
3-4 超分枝狀聚合物之熱性質分析.................................................................. 38
3-4.1 TGA分析................................................................................................... 38
3-4.2 DSC分析................................................................................................... 39
3-5 超分枝狀聚合物之高分子光學性質.......................................................... 40
3-5.1 UV與PL分析............................................................................................ 40
3-5.2 穩定度之PL分析..................................................................................... 40
3-6 超分枝狀聚合物之相對量子效率.............................................................. 44
3-7 超分枝狀聚合物之CV分析....................................................................... 45
3-8 超分枝狀聚合物之EL分析........................................................................ 46
第四章 結論............................................................................................................... 49
4-1 模型化合物.......................................................................................................... 49
4-2 超分枝狀聚合物.................................................................................................. 49
參考文獻..................................................................................................................... 51
附錄圖......................................................................................................................... 54
圖目錄
圖1-1 高分子結構之四種主要分類........................................................................... 1
圖1-2 樹突狀類高分子............................................................................................... 2
圖1-3 工業應用超分枝狀聚合物............................................................................... 2
圖1-4 發散法(divergent)和收斂法(convergent)......................................................... 4
圖1-5 AB2型單體之超分枝狀聚合物......................................................................... 5
圖1-6 A 2 + B 3型單體之超分枝狀聚合物.................................................................. 6
圖1-7 “ AA’ + B’B2”型單體之超分枝狀聚合物......................................................... 7
圖1-8 聚合物之Mw與[η]之關係圖............................................................................ 8
圖1-9 超分枝狀聚合物之應用................................................................................. 10
圖1-10 含三嗪的聚芴超分枝狀聚合物之合成圖式............................................... 10
圖1-11 聚芴超分枝狀聚合物之合成圖式............................................................... 11
圖1-12 含氧二氮雜茂的超分枝狀聚合物之合成圖式........................................... 11
圖1-13 含炔的多環三聚作用之超分枝狀聚合物................................................... 12
圖1-14 PTPQu與PTPTPQu合成示意圖.................................................................. 14
圖1-15 (A)PTPQu與(B)PTPTPQu不同溫度一小時後退火之PL光譜.................. 14
圖1-16 (A)PTPQu與(B)PTPTPQu不同溫度退火後之EL光譜.............................. 14
圖 1-17 PTPQu與PTPTPQu加熱前後退火的發光層元件照片............................. 15
圖3-1 單體之合成圖式............................................................................................. 29
圖3-2 超分枝狀聚合物之模型化合物合成圖式(TPA-3Qu)................................... 29
圖3-3 超分枝狀聚合物之模型化合物合成圖式(TP-2Qu)...................................... 30
圖3-4 超分枝狀聚合物之合成圖式......................................................................... 30
圖3-5 模型化合物之TGA分析(加熱速度20 OC/min) ........................................... 31
圖3-6 模型化合物之UV以及PL光譜(λem: 350 nm)............................................... 32
圖3-7 TP-2Qu加熱退火後一個小時的PL分析(λem: 350 nm)................................. 33
圖3-8 TP-2Qu加熱退火後一個小時的PL分析(λem: 350 nm)................................. 33
圖3-9 TP-2Qu(A)加熱前與(C) 300 OC加熱一小時後的照片以及PA-3Qu(B)加熱
前與(D) 300 OC加熱一小時後的照片.......................................................... 34
圖3-10 TP-2Qu(A)加熱前與(C)300 OC加熱一小時後的照片以及TPA-3Qu(B)加熱
前與(D350 OC加熱一小時後的照片(365nm UV燈照射)............................ 34
圖3-11 TP-2Qu(A)加熱前與(C)300 OC加熱一小時後的光學圖片以及TPA-3Qu(B)
加熱前與(D) 350 OC加熱一小時後的光學圖片.......................................... 34
圖3-12 模型化合物之CV分析................................................................................. 36
圖3-13 超分枝狀聚合物之GPC分析...................................................................... 37
圖3-14 超分枝狀聚合物之TGA分析(加熱速度20 OC/min).................................. 38
圖3-15 超分枝狀聚合物之DSC分析...................................................................... 39
圖3-16 超分枝狀聚合物之UV以及PL光譜(λem: 350 nm)..................................... 40
圖3-17 HB-1加熱退火後一個小時的PL分析(λem: 350 nm)................................... 41
圖3-18 HB-2加熱退火後一個小時的PL分析(λem: 350 nm)................................... 42
圖3-19 HB-3加熱退火後一個小時的PL分析(λem: 350 nm)................................... 43
圖3-20 HB-4加熱退火後一個小時的PL分析(λem: 350 nm)................................... 43
圖3-21 HB-1 (A)加熱前與(C)加熱後270 OC一小時候的照片以及HB-4 (B)加熱前
與(D)加熱後320 OC一小時候的照片........................................................... 43
圖3-22 HB-1 (A)加熱前與(C)加熱後270 OC一小時候的照片以及HB-4 (B)
加熱前與(D)加熱後320 OC一小時候的照片(365nm UV燈照射).............. 43
圖3-23 HB-1 (A)加熱前與(C)加熱後270 OC一小時候的光學圖片以及HB-4 (B)
加熱前與(D)加熱後320 OC一小時候的光學圖片....................................... 44
圖3-24 超分枝狀聚合物之CV分析圖..................................................................... 45
圖3-25 (A)HB-1之EL光譜圖; (B)HB-1元件之I(電流)-V(電壓)-L(亮度)圖......... 47
圖3-26 (A)HB-4之EL光譜圖; (B)HB-1元件之I(電流)-V(電壓)-L(亮度)圖......... 47
圖3-27 (A)HB-1與(B)HB-4分別為室溫與加熱退火後的EL光譜......................... 48
圖3-28 (A)(C)與(B)(D)分別為HB-1和HB-4加熱前後之元件照片....................... 48
表目錄
表1 HB合成所佔莫耳比率....................................................................................... 27
表2 模型化合物量子效率之分析............................................................................ 35
表3 模型化合物之光電學性質................................................................................ 36
表4 超分枝狀聚合物之分子量分析........................................................................ 37
表5 超分枝狀聚合物之重量損失5 %時之裂解溫度.............................................. 38
表6 超分枝狀聚合物量子效率之分析.................................................................... 44
表7 超分枝狀聚合物之光電學性質........................................................................ 46
表8 HB-1和HB-4之元件性質.................................................................................. 48
附錄圖
附錄圖1 TPA-NO2之FTIR光譜圖............................................................................ 54
附錄圖2 TPA-NO2之1H NMR圖譜.......................................................................... 54
附錄圖3 TPA-Bz之FTIR光譜圖.............................................................................. 55
附錄圖4 TPA-Bz之1H NMR圖譜............................................................................. 55
附錄圖5 TPA-Pm之FTIR光譜圖............................................................................. 56
附錄圖6 TPA-Pm之1H NMR圖譜............................................................................ 56
附錄圖7 TP之FTIR光譜圖....................................................................................... 57
附錄圖8 TP之1H NMR圖譜..................................................................................... 57
附錄圖9 TP-NO2之FTIR光譜圖.............................................................................. 58
附錄圖10 TP-NO2之1H NMR圖譜........................................................................... 58
附錄圖11 TP-Bz之FTIR光譜圖............................................................................... 59
附錄圖12 TP-Bz之1H NMR圖譜............................................................................. 59
附錄圖13 TP-Pm之FTIR光譜圖.............................................................................. 60
附錄圖14 TP-Pm之1H NMR圖譜............................................................................ 60
附錄圖15 TP-2Qu之FTIR光譜圖............................................................................ 61
附錄圖16 TP-2Qu之1H NMR圖譜......................................................................... 61
附錄圖17 TPA-3Qu之FTIR光譜圖......................................................................... 62
附錄圖18 TPA-3Qu之1H NMR圖譜........................................................................ 62
附錄圖19 hyperbranched之FTIR光譜圖................................................................. 63
附錄圖20 hyperbranched (HB-1)之1H NMR圖譜.................................................... 63
附錄圖21 hyperbranched (HB-1)之13C NMR圖譜................................................... 64
附錄圖22 hyperbranched (HB-2)之1H NMR圖譜.................................................... 64
附錄圖23 hyperbranched (HB-2)之13C NMR圖譜................................................... 65
附錄圖24 hyperbranched (HB-3)之1H NMR圖譜.................................................... 65
附錄圖25 hyperbranched (HB-3)之13C NMR圖譜................................................... 66
附錄圖26 hyperbranched (HB-4)之1H NMR圖譜.................................................... 66
附錄圖27 hyperbranched (HB-4)之13C NMR圖譜................................................... 67
附錄圖28 hyperbranched (HB-1)之質譜儀分析....................................................... 67
附錄圖29 hyperbranched (HB-2)之質譜儀分析....................................................... 68
附錄圖30 hyperbranched (HB-3)之質譜儀分析....................................................... 68
附錄圖31 hyperbranched (HB-4)之質譜儀分析....................................................... 69

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