以少量的丁二酸二丁酯單體或聚丁二酸二丁酯與丁二酸二乙酯單體或聚丁二酸二乙酯製備共聚酯與混

Minor amounts of monomers or homopolymer of poly(butylene succinate) (PBS) were copolymerized or blended with monomers or homopolymer of poly(ethylene succinate) (PES). PEBSA 95/05 represents a copolymer synthesized from a feed ratio of 95 mol% ethylene glycol and 5 mol% 1,4-butanediol with 100 mol% succinic acid. Copolymers PEBSA 90/10 and 50/50 were also synthesized. Blends of PES and PBS were prepared in solution with ratios of PES/PBS: 98/02, 95/05 and 90/10. Molecular weights of homopolymers and copolymers were measured using capillary viscometer and gel permeation chromatography. The results indicate that polyesters used in this study have high molecular weights. The chemical composition and the sequence distribution of co-monomers in copolyesters were determined using 1H NMR and 13C NMR. The distribution of ES and BS units in these copolyesters was found to be random from the evidence of a single Tg and a randomness value close to 1.0 for a random copolymer. Thermal properties of polyesters and blends were characterized using differential scanning calorimeter (DSC), temperature-modulated DSC (TMDSC) and thermogravimeter. For copolymers, melting point of PES significantly decreases from 100.9 to 94.5 to 89.8 oC with an increasing in BS units from 0 to 5 to 10 mol%. Blends keep the intrinsic melting points of PES and PBS homopolymers. There is no significant difference or no trend about the thermal stability of these polyesters and blends. Wide-angle X-ray diffractograms (WAXD) were obtained for specimens after complete isothermal crystallization. Diffraction peaks indicate that the crystal structure of PES is dominated in PES-enriched copolymers. However, PEBSA 50/50 displays weak diffraction peaks of the characteristic peaks of PBS homopolymer.
Isothermal crystallization of copolyesters and blends were performed using DSC. Their crystallization kinetics and melting behavior after complete crystallization were analyzed. The n1 values of the Avrami exponent for copolyesters increased from 2.54 to 2.84 as the isothermal temperature (Tc) increased. The Hoffman-Weeks linear plots yielded an equilibrium melting temperature of 111.1 and 107.0 oC, respectively, for PEBSA 95/05 and 90/10. Homopolymer PES has an equilibrium melting temperature of 112.7 oC. For blends, the n1 value has a minimum at Tc of 40 oC then it increases with an increase in Tc or in PBS. At the same Tc, n1 increases slightly and the rate constant (k1) decreases when the ratio of PBS in blends increases. All of these blends gave an equilibrium melting temperature of 113.1 oC. Multiple melting behavior involves melting-recrystallization-remelting and various lamellar crystals. As Tc or BS unit in copolymer increases, the contribution of recrystallization slowly declines.
Acetophenone was used a diluent for PES homopolymer. Five concentrations were used to estimate the melting point depression, and the heat of fusion of PES was obtained to have a value of 163.3 J/g according to Flory equation. Spherulitic growth rates of copolymers were measured at Tc between 30 and 80 oC using polarized light microscope (PLM). Maximum growth rates occurred at Tc around 50 oC. It is found that the growth rate of copolymer decreases significantly after randomly incorporating BS units into PES. Non-isothermal method at a cooling rate of 2, 4 or 6 oC/min was used to calculate the isothermal growth rates of copolymers. These continuous data fit very well with the data points measured isothermally. Growth rates data are separately analyzed using the Hoffman-Lauritzen equation. A regime II-III transition is found at 59.4 and 52.4 oC, respectively, for copolyesters PEBSA 95/05 and PEBSA 90/10.
The results of DSC and PLM indicate that blend PES/PBS 98/02 not only retains the melting point and the crystallinity of PES homopolymer, but also increases the nucleation rate of this blend. The effect of blending 2 mol% PBS with PES on the biodegradability of PES is deserved to be investigated furthermore.

目錄…………………………………………………………………………………….I
Scheme Contents……………………………………………………….…………….IV
表目錄……………………………………………………………………………......IV
圖目錄……………………………………………………………………………......VI
摘要………………………………………………………………………………..…XI
Abstract………………………………………………………………………….…XIII
第一章 序論………………………………………………………………………..…1
1.1簡介…………………………………………………………………........1
1.2 研究目的………………………………………………………...………3
第二章 文獻回顧…………………………………………………………………......6
2.1 聚丁二酸二乙酯與聚丁二酸丁二酯的結晶結構…………………...…6
2.2 雙成分聚合物之玻璃轉化溫度……………………………………...…6
2.3 高分子之結晶動力學(crystallization kinetics) ………………...………7
2.3.1 Avrami 方程式……………………………………………........7
2.3.2 多重熔融峰之行為……………………………………………....9
2.3.3 平衡熔點……………………………………………….……….10
2.3.4 區型轉移(regime transition)分析與結晶成長速率…………....10
2.4 偏光顯微鏡………………………………………………………….…12
2.4.1 動態結晶速率分析…………………………………………..…14
2.5溫度調幅式微差掃瞄熱卡儀（Temperature-modulated differential scanning calorimetry , TMDSC）………………………………………14
2.6 熔融熱 (Heat of fusion, delta Hf)…………………………………….15
第三章 實驗…………………………………………………………………………17
3.1 實驗材料…………………………………………………………….…17
3.2 實驗儀器與設備………………………………………………….……17
3.3 樣品製備…………………………………………………………….…18
3.3.1 樣品的純化…………………………………………………..…18
3.3.2 混摻樣品的製備…………………………………………..……19
3.3.3 薄膜試片壓製……………………………………………..……19
3.4 性質檢測分析…………………………………………………….……19
3.4.1 分子量的量測……………………………………………..……19
3.4.2 化學結構分析………………………………………………..…20
3.4.3 玻璃轉移溫度與熔融溫度的量測………………….……….…20
3.4.4 熱穩定性……………………………………………………..…20
3.4.5 晶體結構………………………………………………………..21
3.4.6 PES熔融熱 (delta Hf)…...………………………...……….…...21
3.5 等溫結晶動力學與熔融行為………………………………….………21
3.5.1 等溫結晶動力學分析………………………………………..…21
3.5.2 熔融行為……………………………………………………..…22
3.6 球晶成長速率、型態與區型轉移分析……..……………………….…22
3.6.1 等溫結晶……………………………………………………..…22
3.6.2 動態結晶……………………………………………………..…22
第四章 結果與討論…………………………………………………………………24
4.1 分子量的量測…………………………………………………….……24
4.2 化學結構分析………………………………………...………………..24
4.3 熱性質分析………………………………………………………….…26
4.3.1 玻璃轉移溫度與熔融溫度的量測………………….….………26
4.3.2 熱穩定性分析…………………………………………...……...27
4.3.3 PES熔融熱………………………………………………………27
4.4 晶體結構……………………………………………………………….28
4.5 等溫結晶動力學分析與熔融行為………………………………….…29
4.5.1等溫結晶動力學分析…………………………………………...29
4.5.1.1 PEBSA 95/05……………………………………………29
4.5.1.2 PEBSA 90/10……………………………………………30
4.5.1.3 PES/PBS 98/02………………………………………….30
4.5.1.4 PES/PBS 95/05………………………………………….31
4.5.1.5 PES/PBS 90/10………………………………………….32
4.5.2 熔融行為………………………..........................................……33
4.5.1.1 PEBSA 95/05……………………………………………33
4.5.1.2 PEBSA 90/10……………………………………………34
4.5.1.3 PES/PBS 98/02………………………………………….35
4.5.1.4 PES/PBS 95/05………………………………………….36
4.5.1.5 PES/PBS 90/10………………………………………….36
4.6共聚酯球晶成長速率、型態與區型轉移分析…………...……….……38
4.6.1 PEBSA 95/05等溫結晶之球晶成長速率與區型轉移分析………………………………………………………….…...38
4.6.2 PEBSA 95/05非等溫結晶之球晶成長速率與區型轉移分析………………………………………………………….…...39
4.6.3 PEBSA 95/05結晶形態…………………………………………39
4.6.4 PEBSA 90/10等溫結晶之球晶成長速率與區型轉移分析……40
4.6.5 PEBSA 90/10非等溫結晶之球晶成長速率與區型轉移分析…41
4.6.6 PEBSA 90/10結晶形態…………………………………………42
4.7混摻聚酯相分離結晶型態…………………......................................…42
第五章 結論……………………....................................................................…........44
參考文獻……………................................................................................................116

1. 行政院環保署雙月刊第61期（91年7月）
2. Bikiaris DN, Papageorgiou GZ, Achilias DS. Synthesis and Comparative Biodegradability Studies of Three Poly(alkylene succinate)s. Polym Degrad Stab 2006;91:31-43.
3. Fujimaki T. Processability and Properties of Aliphatic Polyesters,”BIONOLLE”, Synthesized by Polycondensation Reaction. Polym Degrad Stab 1998;59: 209-214.
4. Papageorgiou GZ, Bikiaris DN. Biodegradable Poly(alkylene succinate) Blend: Thermal Behavior and Miscibility Study. J Polym Sci, Part B: Polym Phys 2006;44:584-597.
5. Rizzarelli P, Puglisia C, Montaudob G. Soil Burial and Enzymatic Degradation in Solution of Aliphatic co-Polyesters. Polym Degrad Stab 2004;85:855-863.
6. Yoo Y, Ko MS, Han SL, Kim TY. Degradation and Physical Properties of Aliphatic Copolyesters Derived from Mixed Diols. Polym J 1998;30:538-545.
7. Mochizuki M, Mukai K, Yamada K, Ichise N, Murase S, Iwaya Y, Structural Effects upon Enzymatic Hydrolysis of Poly(butylene succinate-co-ethylene succinate)s. Macromolecules 1997;30:7403-7407.
8. Cao A, Okamurac T, Nakayamab K, Inoued Y, Masudab T. Studies on Syntheses and Physical Properties of Biodegradable Aliphatic Poly(butylene succinate-co-ethylene succinate)s and Poly(butylene succinate-co-diethylene glycol succinate)s. Polym Degrad Stab 2002;78:107-117.
9. Lorenzo MLD. Spherulite Growth Rates in Binary Polymer Blends. Prog Polym Sci 2003;28:663-689.
10. Zhehui L, Mar