聚丁二酸二丁酯 (PBSu)、聚2-甲基-1,3-丁二酸二丙酯 (PMPSu)及其兩種新的共聚酯材料poly(butylene succinate-co-2-methyl-1,3-propylene succinate)s (PBMPSu 95/05 and PBMPSu 90/10)經由兩階段酯化反應製備而成。由1H NMR核磁共振分析儀光譜鑑定出此兩種共聚酯之2-methyl-1,3-propylene succinate (MPS)含量分別為6.5及 10.8 mol%，另並由13C NMR光譜鑑定出此兩種共聚酯為無序排列。本研究利用不同方法探討這些聚酯之非等溫結晶及熱裂解行為，以示差掃描熱量計(DSC)與偏光顯微鏡(PLM)分別在不同降溫速率條件下，研究PBSu及PBMPSu共聚物之非等溫結晶行為，觀察球晶的結晶型態變化及藉由曲線模擬獲得球晶的成長速度，並利用Lauritzen−Hoffman方程式分析區型(regime)轉移溫度，結果得到PBSu、PBMPSu 95/05及PBMPSu 90/10的regime II轉移至regime III 溫度依次為96.2、83.5、77.9 °C。從DSC五種降溫速率之放熱曲線顯示這三種聚酯的非等溫結晶幾乎都發生在regime III。利用modified Avrami、Ozawa、Mo、Friedman 和 Vyazovkin方程式分析DSC數據，所有DSC及PLM分析結果顯示，加入少量的MPS明顯抑制PBSu的結晶。也利用衰減全反射傅立葉轉換紅外線光譜儀(ATR-FTIR)做非等溫結晶行為之探討，發現紅外光譜在918、955、1045 cm-1出現結晶吸收峰。當這些半結晶性聚酯從熔融態開始熔化時，PBSu及其共聚物結晶之紅外線特徵吸收峰，就已經被偵測出。
本研究並利用熱重分析儀連接傅立葉轉換紅外線光譜儀 (TGA-FTIR)及熱裂解氣相層析質譜儀(Py-GC-MS)，探討這些聚酯之熱裂解機制。共聚酯之熱裂解氣體產物經鑑別有酸酐、醚、酯、醇、烯、醛及二氧化碳。經由紅外光譜分析，熱裂解主要產物為酸酐 (anhydride)。此外，透過紅外光譜分析發現共聚酯在裂解溫度低於403°C時，其熱裂解機制與PBSu相同，高於403°C時，其熱裂解機制與PMPSu相同，顯示隨著裂解溫度的升高，MPS在裂解過程中的影響逐漸變大。研究結果顯示，共聚酯(在較低溫度)及PBSu的裂解機制主要依循β氫鍵斷裂機制(β-hydrogen bond scission)及末端基攻擊(back-biting)機制；而共聚酯(在較高溫度)及PMPSu的裂解機制主要依循β氫鍵斷裂機制，其次再依α氫鍵斷裂機制進行。
最後利用TGA在氮氣環境下以1、3、5、10°C/min升溫，探討聚酯之熱裂解動力學及熱穩定性。應用Friedman 及Ozawa此兩種方法，探討在不同熱重損失率下之熱裂解活化能，結果顯示添加少量MPS稍微減少聚酯的熱穩定性。使用兩種Model-fitting方法決定重量損失函數f(α)、活化能及其相關裂解參數。結果顯示自催化級數 (autocatalysis nth-order) 反應機制函數比級數(nth-order)反應機制函數更符合實驗結果。

Poly(butylene succinate) (PBSu), poly(2-methyl-1,3-propylene succinate) (PMPSu), and their two novel poly(butylene succinate-co-2-methyl-1,3-propylene succinate)s (PBMPSu 95/05 and PBMPSu 90/10) were synthesized by a two-stage esterification reaction. PBMPSu 95/05 and PBMPSu 90/10 were characterized as having 6.5 and 10.8 mol% 2-methyl-1,3-propylene succinate (MPS) units, respectively, by 1H NMR. These copolymers were characterized to be random from the 13C NMR spectra. In this study, the nonisothermal crystallization and thermal degradation behaviors of the polyesters were investigated via different approaches. A differential scanning calorimeter (DSC) and a polarized light microscope (PLM) were employed to investigate the nonisothermal crystallization of these copolyesters and neat PBSu. Morphology and the isothermal growth rates of spherulites under PLM experiments at three cooling rates of 1, 2.5 and 5 °C/min were monitored and obtained by curve-fitting. These continuous rate data were analyzed with the Lauritzen-Hoffman equation. A transition of regime II → III was found at 96.2, 83.5, and 77.9 °C for PBSu, PBMPSu 95/05, and PBMPSu 90/10, respectively. DSC exothermic curves at five cooling rates of 1, 2.5, 5, 10 and 20 °C/min show that almost all of the nonisothermal crystallization occurred in regime III. DSC data were analyzed using modified Avrami, Tobin, Ozawa, Mo, Friedman and Vyazovkin equations. All the results of PLM and DSC measurements reveal that incorporation of minor MPS units into PBSu markedly inhibits the crystallization of the resulting polymer. The nonisothermal crystallization behavior of these polyesters was also investigated using a Fourier-transform infrared spectrometer (FTIR) with an attenuated total reflection (ATR). The absorbance peaks of crystals for the α form (918, 955, and 1045 cm-1) of PBSu and PBMPSu copolyesters were observed by ATR-FTIR under nonisothermal crystallization. When these semicrystalline polyesters started to be solidified from the melt state, these characteristic absorption bands for PBSu and its copolyesters crystals have been detected.
In this study, the thermal degradation mechanisms of PBSu, PMPSu, PBMPSu 95/05, and PBMPSu 90/10 were investigated using a thermogravimetric analyzer combined Fourier-transform infrared spectrometer (TGA-FTIR) and a pyrolysis-gas chromatography–mass spectrometry (Py-GC-MS). The volatile products evolved from the thermal degradation of these two copolyesters were identified to be anhydride, ether, ester, alcohol, alkene, aldehyde, and CO2. FTIR spectra displayed that the main degradation products for these four polymers were anhydrides. Moreover, PBSu-rich PBMPSu copolymers exhibited the same thermal degradation mechanism as that of PBSu at lower thermal degradation temperatures (< 403 &#186;C) and as that of PMPSu at higher thermal degradation temperatures (> 403 &#186;C) by the TGA-FTIR analysis. The results of the TGA-FTIR analysis clearly demonstrates that the influence of MPS units on the thermal degradation process is gradually increased as the temperature increases for PBMPSu copolymers. The degradation mechanism of PBMPSu at lower thermal degradation temperatures and PBSu mainly follows the β-hydrogen bond scission mechanism and the back-biting process from the polymer chains. Moreover, the degradation mechanism of PBMPSu at higher thermal degradation temperatures and PMPSu occurred mainly through the β-hydrogen bond scission and secondarily through α-hydrogen bond scission.
Finally, the thermal stability and degradation kinetics of these polyesters were investigated using a TGA at heating rates of 1, 3, 5, and 10 &#186;C/min under dynamic nitrogen. The activation energies of thermal degradation in elective conversions were estimated using the Friedman and Ozawa methods. The results clearly demonstrated that the thermal stabilities of these PBMPSu copolyesters were slightly reduced with the incorporation of minor MPS units into PBSu. Two model-fitting methods of nth-order and autocatalysis nth-order reaction mechanisms were adopted to determine the mass loss function f(α), the activation energy and the associated degradation parameters. The results revealed that the mechanism of autocatalysis nth-order fitted the experimental data much more closely than did the nth-order mechanism for PBSu, PMPSu and PBMPSu copolymers.

論文審定書 ii
誌 謝 iii
摘 要 iv
ABSTRACT vi
CONTENTS ix
LIST OF TABLES xi
LIST OF SCHEMES xii
LIST OF FIGURES xiii
CHAPTER 1 INTRODUCTION 1
1.1. Backgrounds 1
1.2. Motivation and objectives 2
1.3. Research approaches 4
CHAPTER 2 LITERATURE REVIEW AND THEORETICAL APPROACHES 6
2.1. Related researches about poly(butylene succinate) and its copolymers 6
2.1.1. Crystallization structure and conformation of poly(butylene succinate) 6
2.1.2. Related researches of nonisothermal crystallization 7
2.1.3. Related researches of thermal degradation behaviors 11
2.2. Theoretical approaches for nonisothermal crystallization kinetics 13
2.2.1. Avrami model 14
2.2.2. Tobin moldel 15
2.2.3. Ozawa model 15
2.2.4. Mo model 16
2.2.5. Determination of growth rates by the non-isothermal method 17
2.2.6. Kinetic analysis of spherulitic growth rates 17
2.2.7. Effective activation energy 18
2.3. Theoretical approaches for thermal degradation kinetics 19
CHAPTER 3 EXPERIMENTAL 21
3.1. Materials and samples preparation 21
3.2. Experimental instruments 22
3.3. Measurements of copolymer compositions using NMR 23
3.4. Measurements of intrinsic viscosity and molecular weights 23
3.5. Measurements of the spherulitic growth rates using PLM 24
3.6. Evaluation of nonisothermal crystallization behavior using DSC 24
3.7. Evaluation of crystallization behavior using ATR-FTIR 25
3.8. Measuring thermal stability by TGA 25
3.9. Measurements of TGA-FTIR 26
3.10. Measurements of Py-GC-MS 26
3.11. Research procedures 27
CHAPTER 4 RESULTS AND DISCUSSION 29
4.1. Analysis of compositions for PBMPSu copolymers 29
4.2. Molecular weights and thermal properties 30
4.3. Spherulitic growth rates and morphologies 31
4.3.1. Determination of the spherulitic growth rates by the nonisothermal method 31
4.3.2. Kinetic analysis of the spherulitic growth rates 31
4.3.3. Morphologies of spherulites for PBSu and PBMPSu copolymers 32
4.4. Nonisothermal crystallization behavior and kinetics 33
4.4.1. Premolten temperature at 190 °C 33
4.4.1.1. Crystallization behavior and kinetics 33
4.4.1.2. Effective activation energy 38
4.4.2. Influence of various premolten temperatures on crystallization behavior 39
4.5. Nonisothermal crystallization behavior by ATR-FTIR 40
4.6. Thermal degradation mechanisms and kinetics 42
4.6.1. FTIR spectra changes during thermal degradation 42
4.6.2. Evolved gas analysis by Py-GC-MS 46
4.6.3. Thermal degradation mechanisms 48
4.6.4. Thermal degradation kinetics 54
CHAPTER 5 CONCLUSIONS 58
REFERENCES 149

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