本論文探討聚丁二酸二丁酯以及其與少量聚丁二酸二丙酯共聚、混摻物。聚丁二酸二丁酯及以其為主之共聚物本質黏度介於1.62及0.97 dL/g之間；數量平均子量則在2.5x104到11.9x104 g/mol之間，其多分佈指數為1.52至3.94。以核磁共振儀之氫譜及碳譜定量共聚物之不同單體含量及亂度參數，由其單一玻璃轉換溫度及亂度參數之接近於一，可推論本文所探討之共聚物均為無規共聚物。聚丁二酸二丁酯的玻璃轉換溫度為-40.8 °C；隨著二丙酯的成分增加共聚物的玻璃轉換溫度逐漸升高而熔點降低，但在混摻物熔點降低現象較不明顯。
聚丁二酸二丁酯以及其與少量聚丁二酸二丙酯共聚、混摻物的Avrami指數介於2到3之間，推論其結晶為二維的同質成核或三維的異質成核，對聚丁二酸二丙酯、共聚及混摻物升溫可觀察到多重熔融峰。Tm1稱為退火峰，可能是由於升溫過程中熔融與再結晶相互競爭所造成。Tm2則是由主要的層版熔融所造成，並由Hoffman-Weeks線性外插法求得聚丁二酸二丁酯的平衡熔點為127.4 °C;樣品代號PBTSu95/05為125.7 °C；PBTSu90/10為120.6 °C。混摻物代號PBSu/PTSu 98/02的平衡熔點為128.6 °C；PBSu/PTSu 95/05為127.0 °C；PBSu/PTSu 90/10為125.5 °C其增厚係數( )介於0.77至0.8。
由熱重分析儀實驗測得樣品熱裂解三個特徵溫度分別為，熱裂解起始溫度(Tstart)、質量損失2%的溫度(Tloss2%)及裂解最快的溫度(Tmax)。由於PBTSu90/10較高的分子量，使其熱裂解起始溫度及質量損失2%的溫度較其他樣品有明顯不同。
將樣品於不同等溫條件下製備，由廣角X光繞射實驗所得到的繞射峰位置不隨溫度改變，但溫度增加將使繞射逐漸變得尖銳且涵蓋的面積增加，推測其升溫過程中晶格不會發生改變，其晶點(crystallite)變大且較為完美。聚丁二酸二丁酯的球晶成長速率在103 °C時為0.01 μm/sec隨著結晶溫度下降迅速增加於75 °C時為3.33 μm/sec。在增加二丙酯成份後，其球晶成長速率也會大量減少，推測其中之一原因可能於結晶過程中二丙酯阻礙了其分子鏈的疊加。將球晶成長速率以Lauritzen-Hoffman二次成核理論加以分析，採用Williams-Landel– Ferry模型可計算出聚丁二酸二丁酯由regimeII轉移到regime III的溫度為95.1 °C；PBTSu95/05和PBTSu90/10分別為84.4及77.1 °C。
本文所使用的樣品於偏光顯微鏡下觀察皆為二維且較相似於軸晶，觀察其雙折射率現象，可歸類為負光性球晶。在較大過冷度(supercooling)下結晶，可以觀察到消光環的現象。

A small amount of poly(trimethylene succinate) (PTSu) were copolymerized or blended with poly(butylenes succinate) (PBSu) in this study. The range of intrinsic viscosity for PBSu and PBSu-enriched copolymers are between 1.62 and 0.97 dL/g; number-average molecular weights are in the range of 2.5x104 and 11.9x104 g/mol with polydispersity indices ranging from 1.52 to 3.94. Copolymer composition is calculated from 1H and 13C NMR spectra, and the distribution of BS and TS units in these copolymers are supported to be random from the evidence of a single glass transition temperature (Tg) and a randomness value close to 1.0. Tg of PBSu is -40.8 °C. The Tg values of copolymers and blends increased with TS contents. The melting temperature (Tm) and the exothermic heat of crystallization of blends were not strongly affected by blending with PTSu.
The values of Avrami exponent (n) for PBSu, copolymers and blends ranging from 2.3 to 3.1 indicate that heterogeneous nucleation with three-dimensional growth and homogeneous nucleation with two-dimensional growth might happen during the crystallization process. Multiple melting behavior was observed for PBSu, PBSu- enriched copolyesters and blends. Their peak temperatures are denoted as Tm1, Tm2 and Tm3 in order of increasing temperature. Tm1 corresponds to the melting temperature of the so-called annealing peak which might be resulted from the competition between continuous melting and re-crystallization. In contrast the peak at Tm2 is attributed to the melting of the primary crystals formed during isothermal crystallization. The peak at Tm3 may arise from the melting of re-crystallized primary crystals. Equilibrium melting temperatures were determined by the Hoffman-Weeks linear extrapolations which yield of 127.4 °C for PBS, 125.7 °C for PBTSA95/05, 120.6 °C for PBTSu90/10, 128.6 °C for PBSu/PTSu 98/02, 127.0 °C for PBSu/PTSu 95/05 and 125.5 °C for PBSu/PTSu 90/10. The thickness coefficient ( ) is located between 0.77 and 0.80.
Three characteristics temperatures of thermal degradation, defined as temperature of thermal degradation at begining (Tstart), weight losses of 2% (Tloss2%) and maximum degradation rate (Tmax), were employed to characterize the thermal stability of polyesters and blends. The Tloss2% and Tstart values of PBTSu90/10 are higher than the values of the others because of its unusually high molecular weight.
Wide-angle x-ray diffraction patterns were obtained after complete isothermal crystallization. Diffraction peaks are in the same positions, and these peaks become sharper and increase in intensity as the crystallization temperature increases. This indicates that during the heating process, only one crystal form appears and both of the crystallite size and perfect degree increase. The isothermal growth rate of PBSu spherulite increases from 0.01 μm/sec at 103 °C to 3.33 μm/sec at 75 °C. When the TS units increase, the spherulitic growth rates of PBTSu95/05 and PBTSu90/10 copolyesters decline dramatically. One of the reasons is that the incorporation of TS units into PBSu significantly inhibits the crystallization behavior of PBSu. Growth rates data were treated with Lauritzen-Hoffman secondary nucleation theory to find the regime transition. Using the Williams-Landel-Ferry (WLF) values, regime II to III transition is found at 95.1 °C for PBSu, 84.4 °C PBTSu95/05, and 77.1 °C for PBTSu 90/10. All melt-crystallized specimens formed two dimensional axial-like spherulites with negative birefringence. Extinction bands were observed when PBSu, PBSu- enriched copolymers and blends specimens were crystallized at large undercooling.

List of tables………………...……………………………………………………..iv
List of schemes…………….……………………………………………………….vi
List of figures…………………...………………………………………………….vi

摘要…………………………………………………………………………………xiii
Abstract………………………………………………………………………..…....xv
1 Introduction…………………………………………………………………….1
1.1 Background……………………………………………………….……..1
1.2 Factors affecting biodegradation………………………………...……..…6
1.3 Applications…………………………………………………….…….….7
1.4 Motivation……………………………………………………….….…….7

2. Literature review…………………………………………….…...…..…………...9
2.1 Crystallization kinetics analyses……………………………...……………9
2.1.1 Avrami equation…………………………………………………..9
2.1.2 Dynamic growth rate……………………………………………10
2.1.3 Regime transition analysis…………………………..………….11
2.2 Kinetics and thermodynamics of fusion…………………………………13
2.2.1 Multiple melting behaviors…………………………...….……..13
2.2.2 Hoffman-Weeks linear extrapolation………………..…………15
2.3 Fox equation……………………………………………………...………..16
2.4 Polarized light microscopy………………………………………..………16

3. Experimental…………………………………………………………………19
3.1 Materials. ……………………………………………………………19
3.2 Samples preparation………………………………………………19
3.3 Instruments……………………………………………………………20
3.4 Characterization and measurements………………………………20
3.4.1 Analyses of chemical structures…………….…………………..20
3.4.2 Measurements of molecular weights………………..………….21
3.4.3 Measurements of Tg and Tm…………………………………..21
3.4.4 Thermal stability…………………………..…………………….22
3.4.5 Wide-angle X-ray diffraction…………………………………...22
3.4.6 Crystallization kinetics and melting behaviors……….……….22
3.4.6.1 Kinetics of isothermal crystallization…………...…...22
3.4.6.2 Observation of melting behaviors by DSC……….….23
3.4.7 Crystal morphology and measurement of growth rate.............23
3.4.7.1 Isothermal growth rate…………………….………….23
3.4.7.2 Dynamic growth rate………………………………….23
3.4.8 Microscopy of PBSu and PBTSu……………………….………24
3.4.8.1 SEM microscopy…………………...……...…….…….24
3.4.8.2 AFM microscopy…………………...……...…………..24

4. Results and discussion……………………………………………...…...……….25
4.1 Intrinsic viscosity and molecular weights..………………………………25
4.2 Analyses of chemical structures…………………………………………..25
4.3 Measurements of Tg and Tm…………..……………………….………….28
4.4 Kinetics of isothermal crystallization…………………………...……….29
4.5 Melting behaviors and equilibrium melting temperature……………...31
4.6 Thermal stability……………………………...…………………………...34
4.7 Crystal structure…………………………………………………...……...34
4.8 Growth rate and regime transition…………………………...…...……..35
4.9 PLM, SEM and AFM micrographs……………………...….......………..35

5. Conclusions…………….. ………………………………………………………..39
Reference…………………………………………..………………..…………...118

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