在本實驗中主要探討聚丁二酸二乙酯(PES)、聚丁二酸二丙酯(PTS)以及其不同成分比例的共聚酯(PETSAs)結構與性質間之關係。由凝膠滲透層析儀(GPC)與毛細管黏度計測量結果顯示聚酯擁有足夠大的分子量；且利用1H及13C核磁共振分析儀(NMR)定量共聚酯的組成，並以13C-NMR檢測共聚酯內單體的排列順序為無規的分佈；而後使用微差式掃瞄熱卡儀(DSC)討論聚酯之熱性質；利用熱重分析儀(TGA)與偏光顯微鏡(PLM)，在氮氣環境下，觀察熱分解的起始溫度，由TGA結果顯示各個樣品間熱穩定性相似(Tsta t:246±3 °C)，但使用PLM測量PES
與PETSA(95/05)在不同預熔融溫度下熔融後，觀察等溫結晶時成長速率的變
化，判斷出裂解溫度分別為213 °C 以及200 °C 其靈敏度較TGA 來的好，而加
入5 mol%的TS 即會降低其熱穩定性；接著討論共聚酯在低於熔點5~10 °C 作等
溫結晶後，以X 光繞射分析儀(WAXD)觀測其晶體結構。由WAXD以及DSC 的
結果顯示當TS 加入PES，會輕微抑制其共聚酯的結晶行為。
在實驗的第二部分，針對PES 以及PETSA(95/05)作詳細的討論。利用DSC
研究結晶動力學與熔融行為，且使用溫度調幅式微差掃描熱卡儀(TMDSC)同時
分析可逆、整體與不可逆的熱分析曲線。以Hoffman-Weeks 線性外插法求得PES
以及PETSA(95/05)的平衡熔點(Tm
0)分別為112.7 °C 與108.3 °C；從樣品在不同
等溫結晶溫度下之WAXD 圖譜得知，樣品在此溫度範圍下只存在一種結晶形
式。由DSC、TMDSC 以及WAXD 結果得知，多重熔融峰產生的原因是由雙形
態和熔融-再結晶-再熔融兩種熔融機構所影響；最後使用PLM 觀察樣品球晶成
長速率與結晶形態，分別以等溫結晶與非等溫結晶兩種實驗方法測量其成長速
率，結果顯示所得成長速率數據相近，除此之外，由非等溫結晶實驗所得成長速
率溫度範圍更廣且實驗時間大大縮短。在regime II®III 轉移溫度方面，PES 大
約是71 °C 其值與文獻相近，而PETSA(95/05)則大約65 °C。

Poly(ethylene succinate) (PES), poly(trimethylene succinate) (PTS) and their copolyesters (PETSAs) with various compositions were used to investigate the structure-property relationship. The results of intrinsic viscosity and GPC have proven successful in preparing high molecular weight polyesters. The chemical compositions and the sequence distribution of co-monomers in the copolyesters were determined by NMR spectroscope. The distributions of ES unit and TS unit were found to be random. Their thermal properties were characterized using differential scanning calorimeter (DSC). The thermal stability of polyesters was analyzed by thermogravimeter (TGA) and polarized light microscope (PLM) under nitrogen. The results of TGA show that all of the samples have similar thermal stability (Tstart : 246±3 °C), but the thermal
degradation temperature of PES and PETSA(95/05) are 213 and 200 °C, respectively,
estimated from the isothermal growth rates after pre-melting at various temperatures.
The degradation temperature analyzed by PLM is more sensitive than that obtained
from TGA. The incorporation of 5 mol% of TS units into PES significantly reduces
the thermal stability of PES. In addition, wide-angle X-ray diffractograms (WAXD)
were obtained for polyesters which were crystallized isothermally at a temperature
5~10 °C below their melting temperatures. The results of WAXD and DSC indicate
that the incorporation of TS units into PES significantly inhibit the crystallization
behavior of PES.
In the second part of this study, PES and PETSA(95/05) were studied in detail.
The crystallization kinetics and the melting behavior were investigated by using DSC
in both conventional mode and modulated mode (TMDSC). The reversing, total, and
non-reversing heat flow curves were analyzed. The Hoffman-Weeks plots gave an
equilibrium melting temperature of 112.7 and 108.3 °C for PES and PETSA(95/05),
XI
respectively. Only one crystal form was found from WAXD for specimens crystallized
isothermally at various temperatures. Based on the WAXD patterns, DSC and
TMDSC thermograms, multiple endothermic melting peaks can be explained by two
mechanisms, melting-recrystallization-remelting and dual morphologies. PLM was
used to study the growth rates and morphology of the spherulites. The growth rates
measured in isothermal conditions were very well comparable with those measured by
the non- isothermal procedure. In addition, the temperature range of growth rates
detected by the non- isothermal procedure is wider than that by the isothermal method,
which is time consuming. The regime II®III transition of PES was estimated at ~ 71
°C which is very close to the literature values, and that of PETSA(95/05) was found at
~ 65 °C.

目錄
目錄 I
表目錄 III
Scheme Contents III
圖目錄 IV
摘要 IX
Abstract X
第一章 緒論 1
1.1 簡介 1
1.2 研究目的 2
1.3 實驗流程圖 2
第二章 文獻回顧 5
2.1 高分子之結晶動力學 (crystallization kinetics)： 5
2.1.1 Avrami 方程式 5
2.1.2 多重熔融峰之行為(multiple endotherm behaviors) 6
2.1.3 平衡熔點 7
2.1.4 以球晶成長速率作區型轉移(regime transition)分析 8
2.2 偏光顯微鏡 10
2.2.1 非等溫結晶分析 13
2.3 溫度調幅式微差掃描熱卡儀 (Temperature-modulated differential scanning calorimetry，TMDSC) 13
第三章 實驗 15
3.1 實驗材料 15
3.2 實驗儀器與設備 15
3.3 檢測分析 16
3.3.1 分子量測量 16
3.3.2 化學結構分析 17
3.3.3 樣品的製備 17
3.3.4 玻璃轉移溫度(Tg)與熔融溫度(Tm)之量測 17
3.3.5 熱穩定性質 18
3.3.6 晶體結構 18
3.4 結晶動力學分析與熔融行為 18
3.4.1 WAXD分析 18
3.4.2 等溫結晶動力分析 18
3.4.2.1 等溫結晶(傳統模式) 19
3.4.2.2 熔融行為(調幅模式) 19
3.5 結晶形態、成長速率及區型轉移分析 19
3.5.1 等溫結晶 20
3.5.2 非等溫結晶 20
第四章 結果與討論 21
4.1 分子量測量 21
4.2 化學結構分析 21
4.3 熱性質分析 23
4.3.1 熔融溫度(Tm)之量測 23
4.3.2 玻璃轉移溫度(Tg)之量測 24
4.4 熱穩定性質 25
4.4.1熱重分析儀 25
4.4.2以偏光顯微鏡作熱穩定性分析 25
4.5 晶體結構 26
4.6 結晶動力學分析與熔融行為 26
4.6.1 PES與PETSA(95/05)之WAXD分析 26
4.6.2 PES之等溫結晶動力分析 26
4.6.3 PES之熔融行為 27
4.6.4 PETSA(95/05)之等溫結晶動力分析 28
4.6.5 PETSA(95/05)之熔融行為 29
4.7 結晶形態、成長速率與區型轉移分析 30
4.7.1 PES等溫結晶之球晶成長速率與區型轉移分析 30
4.7.2 PES非等溫結晶之球晶成長速率與區型轉移分析 31
4.7.3 PES之結晶形態觀察 33
4.7.4 PETSA(95/05)共聚酯等溫結晶之球晶成長速率與區型轉移分析 34
4.7.5 PETSA(95/05)共聚酯非等溫結晶之球晶成長速率與區型轉移分析 35
4.7.6 PETSA(95/05)之結晶形態觀察 37
第五章 結論 39
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