臺灣博碩士論文加值系統

本研究主要探討芳香族聚酯中，萘環與苯環以及亞甲基數量的差異，對共聚酯的熱穩定性、熱性質及結晶結構，所造成的影響。實驗以對苯二甲酸丁二酯(Poly(butylene Terephthalate), PBT)、2, 6-萘二甲酸丁二酯(Poly(butylene 2,6-naphthalate), PBN)及2, 6-萘二甲酸乙二酯(Poly(ethylene 2,6-naphthalate), PEN)為材料，再以90:10的莫耳比組成共聚酯PBT-co-PBN (BTBN)、PBT-co-PEN (BTEN)及PEN-co-PBN (ENBN)。以核磁共振儀(Nuclear Magnetic Resonance, NMR)、熱重分析儀(Thermalgravimetric Analyzer, TGA)、微差掃描熱分析儀(Differential Scanning Calorimeter, DSC)及廣角X光繞射儀(Wide-angle X-ray Diffraction, WAXD)分析共聚酯的組成含量、熱穩定性、結晶行為及結晶結構。
NMR結果顯示，共聚反應的餵料比與共聚酯的實際組成是差不多的。TGA結果顯示，萘環結構的失重速率峰值溫度(Tdp)較苯環結構高，故萘環的熱穩定性較苯環佳。非等溫WAXD實驗結果顯示，組成成分較多的單元主導共聚酯的結晶結構。透過DSC觀察發現，ENBN共聚酯的結晶熱焓再加入PBN單體後大幅下降，再次升溫可以觀察到再結晶現象，因此判斷以ENBN共聚酯紡絲，則須再額外進行熱處理。等溫WAXD實驗結果顯示，PBN在230 °C下出現新的結晶峰，BTBN共聚合物在210 °C下出現PBN的α-form結晶峰。ENBN的(1̅12)和(1̅11)衍射峰值逐漸顯著,結晶度也增加。與BTBN相比，BTEN的結晶度下降更多，這表明BN鏈段比EN鏈段更容易在共聚酯中結晶。

This study mainly discusses the effects of naphthalene ring, benzene ring, and methylene group on the thermal stability, thermal properties, and crystal structure of aromatic copolyesters. Poly(butylene terephthalate) (PBT), poly(butylene 2,6-naphthalene dicarboxylate) (PBN), and poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) were used to prepare a molar ratio of 90:10 PBT-co-PBN (BTBN), PBT-co-PEN (BTEN), and PEN-co-PBN (ENBN) copolyesters. Nuclear magnetic resonance (NMR), thermalgravimetric analyzer (TGA), differential scanning calorimeter (DSC), and wide-angle x-ray diffraction (WAXD) were used to analyze the composition content, thermal stability, crystallization behavior, and crystal structure of copolyesters.
NMR results show that the feed ratio of the copolymerization reaction is similar to the actual composition of the copolyesters. TGA results show that Tdp of the naphthalene ring is higher than the benzene ring, so the thermal stability of the naphthalene ring is better than that of the benzene ring. DSC results show that exothermic enthalpy of ENBN copolyesters decreased significantly after adding PBN monomer. The reheating curve of DSC can observe the recrystallization behavior of copolyesters. WAXD results show that the main components dominates the crystal structure of the copolyesters. PBN appear new crystallization peaks at 230 ℃, and BTBN copolyesters appear α-form crystallization peaks of PBN at 210 ℃. The (1 ̅12) and (1 ̅11) diffraction peak of ENBN gradually significant, and the crystallinity also increase. Compared with BTBN, the crystallinity of BTEN drops more, which indicated that the BN segment is easier to crystallize in the copolyesters than the EN segment.

目錄
誌　　謝 I
摘　　要 II
ABSTRACT III
圖目錄 V
表目錄 VII
符號對照表 VIII
第一章 緒論 4
1.1. 前言 4
1.2. 分子鏈段柔軟性 4
1.3. 高分子多重熔融峰現象 4
1.4. 共聚物之序列結構 5
1.5. POLY(BUTYLENE TEREPHTHALATE) (PBT)聚對苯二甲酸丁二酯的發展 6
1.5.1. PBT 結晶結構XRD繞射圖 8
1.5.2. PBT的結晶熔融行為 9
1.5.3. PBT等溫結晶生長樣貌 10
1.6. POLY(BUTYLENE-2,6-NAPHTHALATE) (PBN)聚萘二甲酸丁二酯的發展 11
1.6.1. PBN熱處理後的結晶結構圖譜 14
1.6.2. PBN的多重熔融現象 15
1.7. POLY(ETHYLENE-2,6-NAPHTHALATE) (PEN)聚萘二甲酸乙二酯的發展 16
1.7.1. PEN結晶結構XRD繞射圖 18
1.7.2. PEN等溫結晶生長樣貌 19
1.7.3. PEN的多重熔融峰現象 20
1.8. 共聚酯的發展 21
1.8.1. PBT/PEN 共混物的熱性質 21
1.8.2. PET-co-PEN 共聚酯相容性及熱性質 22
1.8.3. 不同熱處理程序下PET-co-PEN 共聚酯纖維的熱性質 24
1.8.4. 不同熱處理程序下PET-co-PEN 共聚酯纖維的力學性質 25
1.8.5. PET/PEN共聚酯纖維斷面與表面型態觀察 26
1.8.6. PEN-co-PBN共聚酯的熱性質 27
1.8.7. PEN-co-PBN共聚酯的結晶結構 28
1.9. 研究動機與目的 29
第二章 實驗 30
2.1. 實驗材料 30
2.2. 實驗流程 31
2.3. 實驗儀器與方法 32
2.3.1. 核磁共振儀(Nuclear Magnetic Resonance, NMR) 32
2.3.2. 微差掃描熱分析儀(Differential Scanning Calorimeters, DSC) 32
2.3.3. 廣角X光繞射儀(Wide Angle X-ray Diffraction, WAXD) 34
第三章 結果與討論 35
3.1. 序列結構分析 35
3.1.1. 共聚酯1H-NMR化學位移標定 35
3.1.2. 共聚酯13C-NMR化學位移標定 41
3.2. 非等溫結晶行為熱分析 47
3.3. 非等溫裂解行為 50
3.4. 晶面結構分析 52
3.3.1. 非等溫結晶結構 52
3.3.2. 等溫結晶結構 58
第四章 結論 64
參考文獻 66

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