臺灣博碩士論文加值系統

在本篇論文中，成功製備了4,4'-(quinoxaline-2,3-diyl) diphenol / furfurylamine-based- benzoxazine（QDP-fu）及4,4',4',4'-([6,6'-biquinoxaline]-2,2',3,3'-tetrayl)tetraphenol/furfurylamine-based benzoxazine（BQTP-fu）。
前驅物4,4'-(quinoxaline-2,3-diyl)diphenol（QDP）和4,4',4',4'-([6,6'-biquinoxaline]-2,2',3,3'-tetrayl)tetraphenol（BQTP），經由4,4'-二羟基二苯基乙二酮(4,4-dihydroxybenzil)與鄰苯二胺和3,3-二氨基聯苯胺的縮合製備。
通過FTIR，1H和13C-NMR圖譜證實了QDP-fu和BQTP-fu的結構。根據QDP-fu和BQTP-fu的DSC熱分析圖，熔點為65和102℃，放熱峰分別為228和225℃，顯示出兩個benzoxazine結構的優異加工性。根據DMA熱譜圖中tanδ的峰值溫度，QDP-fu的熱固性Tg為329.1℃，QDP-fu的熱固性Tg為418.6℃。
結果顯示可以在兩種benzoxazine中同時實現高性能和良好的可加工性。

In this thesis, a 4,4'-(quinoxaline-2,3-diyl)diphenol/furfurylamine-based- benzoxazine (QDP-fu) and a 4,4',4',4'-([6,6'-biquinoxaline]-2,2',3,3'-tetrayl)tetraphenol/furfurylamine-based benzoxazine (BQTP-fu) were prepared.
The precurosrs 4,4'-(quinoxaline-2,3-diyl)diphenol (QDP) and 4,4',4',4'-([6,6'-biquinoxaline]-2,2',3,3'-tetrayl)tetraphenol (BQTP) were prepared from the condesnation of 4,4-dihydroxybenzil with o-phenylenediamine and 3,3-diaminobenzidine, respectively. The structure of QDP-fu and BQTP-fu were successfully confirmed by FTIR, 1H and 13C-NMR spectra.
According to the DSC thermograms of QDP-fu and BQTP-fu, the melting point is 65 and 102 oC, the exothermic peak is 228 and 225 oC, respectively, showing a wide processing window for both benzoxazine.
According to the the peak temperature of tanδ in the DMA thermogram, Tg of thermoset of QDP-fu and is 329 oC, whild no glass transition was observed for thermoset of BQTP-fu before 400 oC.
As a result, high-performance and good processability can be achieved simultaneously in both benzoxazines.

第一章 緒論 1
第二章 文獻回顧 2
2.1 喹喔啉(Quinoxaline)與聚喹喔啉(Polyquinoxaline)合成發展 2
2.2 氧代氮代苯并環己烷(Benzoxazine, Bz)的合成發展 5
2.3 Bz開環聚合文獻 8
2.4 喹喔啉(Quinoxaline)衍生之Bz文獻 14
2.5 2-呋喃甲胺衍生之Bz文獻 17
2.6 研究動機 24
第三章 實驗內容 25
3.1 實驗藥品與溶劑 25
3.1.1 藥品 25
3.1.2 溶劑 26
3.2 實驗儀器 27
3.3 實驗步驟 29
3.3.1 單體4,4-Dihydroxybenzil合成 29
3.3.2 單體QDP合成 30
3.3.3 單體QDP-fu合成 31
3.3.4 單體BQTP合成 32
3.3.5 單體BQTP-fu合成 33
3.3.6 Bz固化物製備 34
第四章 結構鑑定與分析 35
4.1 4,4-Dihydroxybenzil光譜鑑定與分析 35
4.2 QDP光譜鑑定與分析 36
4.2.1 1H NMR鑑定 36
4.2.2 13C NMR 鑑定 38
4.3 QDP-fu光譜鑑定與分析 40
4.3.1 1H NMR鑑定 40
4.3.2 13C NMR 鑑定 42
4.3.3 傅立葉轉換紅外線光譜(FTIR)鑑定 44
4.4 BQTP光譜鑑定與分析 45
4.4.1 1H NMR鑑定 45
4.4.2 13C NMR 鑑定 47
4.5 BQTP-fu光譜鑑定與分析 49
4.5.1 1H NMR鑑定 49
4.5.2 13C NMR 鑑定 51
4.5.3 傅立葉轉換紅外線光譜(FTIR)鑑定 53
第五章 結果與討論 54
5.1 單體QDP-fu之合成探討 54
5.2 Bz之DSC分析 55
5.3 Bz固化變溫FTIR追蹤 60
5.4 Bz固化物機構探討 63
5.5 Bz之膠化時間(Gel time)測定 65
5.6 熱性質分析 67
5.6.1 TMA之分析 67
5.6.2 DMA之分析 69
5.6.3 TGA之分析 70
第六章 結論 72
第七章 參考文獻 73

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