本文所用之樣品為工研院化工所所提供，為聚對苯二甲酸乙二酯（PET）與聚對苯二甲酸丙二酯（PTT）之共聚酯，其樣品代號分別為C2∼C4，經H1與C13 NMR定量分析其成分，可知其在共聚酯內ET單體的組成個別為8.9、33.7、37.9％，而PT單體為91.1、66.3、62.1％。

以微差掃描卡儀（Differential scanning calorimeter，DSC）探討等溫結晶動力和熔融行為及偏光顯微鏡（Polarizing Microscope，PLM）觀察其球晶成長速率和結晶形態。C2、C3、C4其平衡熔點(Tmo ) oC經Hoffman-Weeks線性理論及M-X非線性理論的分析為(240.6、275.5)、(208.8、247.0)、(194.3、229.4)。不同樣品在不同結晶溫度(Tc) oC下所求得之球晶成長速率(μm/s )為C2(180~207，0.614~0.061)、C3(130~166，0.112~0.021)、C4(120~160，0.0213~0.003)。

由不同的平衡熔點和不同T∞值 (Tg -30.0、Tg -51.6 oC)分析其區型轉移溫度TⅡ→Ⅲ時，可得C2(234.0、237.1、240.6、275.5，195.9±0.3, 196.2±0.4)、C3(193.1、198.9、208.8、247.0，147.5±0.2, 147.5±0.1)、C4(184.1、187.9、194.3、229.4，133.3±0.4, 133.6±0.2)。比較此結果與由DSC以結晶完成一半所需的時間(t1/2)代替球晶成長速率G所得之結果(C2(193.6 oC)、C3(147.3 oC)、C4(1140.4 oC))。可發現C2略高2.3~2.6 oC，C3的結果相差不遠，C4略低於6.8~7.1 oC。

從球晶圖譜上的形態和區型轉移溫度(TⅡ→Ⅲ) oC，可知在接近區型轉移溫度時其形態上會產生變化。C2球晶在結晶溫度180∼196 oC之間為規則性的球晶，而在結晶溫度197∼208oC之間有環狀消光條紋產生。其條紋間距隨著結晶溫度的升高而增加。C3球晶在結晶溫度130∼147 oC之間為規則性的球晶，而在結晶溫度148∼172oC之間有環狀消光條紋產生。其條紋間距隨著結晶溫度的升高而增加。C4球晶在結晶溫度120∼134 oC之間為規則性的球晶，而在結晶溫度135∼160oC之間有環狀消光條紋產生。其條紋間距隨著結晶溫度的升高而增加。

結合M-X plot及偏光顯微鏡所觀察到的照片及以80 oC/min加熱得到的熔融峰的結果，可知C2在結晶溫度210∼213oC之間，應為Regime Ⅰ→Ⅱ轉移溫度範圍，C3在結晶溫度174∼178oC之間，應為Regime Ⅰ→Ⅱ轉移溫度範圍，C4在結晶溫度160∼164oC之間，應為Regime Ⅰ→Ⅱ轉移溫度範圍。

C3之熔解熱(△Hu) 由實驗結果可得為4.88±0.06 kcal/mol，B值為1.47±0.05 cal/c.c；C4之熔解熱(△Hu) 由實驗結果可得為2.56±0.22 kcal/mol，B值為4.45±0.36 cal/c.c。此結果與PET之熔解熱(△Hu)5.6 kcal/mol及PTT之熔解熱(△Hu)7.2 kcal/mol比較，其中PTT > PET > C3> C4。

These developmental grade samples were supplied by the Union Chemical Laboratories of Industrial Technology Research Institute(ITRI). The compositions of a series of copolyesters were identified by C1-NMR and H1-NMR. The ethylene terephthalate(ET) units are 8.9、33.7、37.9% and trimethylene terephthalate(PT) units are 91.1、66.3、62.1% in the copolyesters with sample codes of C2、C3、C4.

Differential scanning calorimeter(DSC) was used to study the isothermal crystallization kinetics and melting behaviors and Polarizing Microscope(PLM) was used to study the spherulite growth rates and spherulite patterns. The Hoffman-Weeks linear plot and M-X nonlinear plot gave an equilibrium meiting temperature(Tmo ) oC of C2、C3、C4 are (240.6、275.5)、(208.8、247.0)、(194.3、229.4). The growth rates (μm/s )of different samples in the different crystallination temperature(Tc) oC are C2(0.614~0.061, 180~207)、C3(0.112~0.021, 130~166)、C4(0.0213~0.003, 120~160).

From the different equilibrium meiting temperature(Tmo ) and different T∞ = ( Tg-30, Tg-51.6 oC) to analysis the regime transition temperature (TⅡ→Ⅲ) in units of oC are C2(234.0、237.1、240.6、275.5，195.9±0.3, 196.2±0.4)、C3(193.1、198.9、208.8、247.0，147.5±0.2, 147.5±0.1)、C4(184.1、187.9、194.3、229.4，133.3±0.4, 133.6±0.2). Compare the results with the results that using the half-time of crystallization(t1/2) from DSC (C2(193.6 oC)、C3(147.3 oC)、C4(1140.4 oC)). It can find that C2 is over 2.3 and 2.6 oC and C3 is the same and C4 is under 6.8 and 7.1 oC.


From the morphology of spherulite patterns and regime transition temperature (TⅡ→Ⅲ) oC, the results indicated that the change from the morphology is closed to regime transition temperature. Regular spherlites were exhibited at temperature(Tc) between 180 and 196 oC and banded spherulites were observed between 197 and 208 oC in the C2. The band spacing increase with increasing crystallization temperature. Regular spherlites were exhibited at temperature(Tc) between 130 and 147 oC and banded spherulites were observed between 148 and 172 oC in the C3. The band spacing increase with increasing crystallization temperature. Regular spherlites were exhibited at temperature(Tc) between 120 and 134 oC and banded spherulites were observed between 135 and 160 oC in the C4. The band spacing increase with increasing crystallization temperature.

Combine the results of M-X plot and spherulites pattern and melting behaviors at a heating rate of 80 oC/min . It indicated that the regime transition temperature (TⅠ→Ⅱ) oC are in the range of crystallization temperature of C2、C3、C4 are (210~213、174~178、160~164 oC).

The heat of fusion (△Hu) of C3 is 4.88±0.06 kcal/mol and B is 1.47±0.05 cal/c.c from the experimental. The heat of fusion(△Hu) of C4 is 2.56±0.22 kcal/mol and B is 4.45±0.36 cal/c.c from the experimental. Compare the results with PET(△Hu = 5.6 kcal/mol) and PTT(△Hu = 7.2 kcal/mol). It indicated that PTT > PET > C3 > C4.

摘要 I
Abstract III
表目錄 V
圖目錄 VII
第一章 導論 1
1-1 簡介 1
1-2 研究目的 3
第二章 文獻回顧與相關理論 4
2-1 高分子之結晶動力學(crystallization kinetics) 4
2-1-1 區型轉移 (Regime transition) 分析和結晶成長速率 4
2-1-2 多峰熔融之行為 7
2-1-3 平衡熔點 8
2-1-4熔解熱(heat of fusion) (△Hu) 13
2-2 偏光顯微鏡 15
第三章 實驗 21
3-1 實驗材料 21
3-2 實驗儀器與設備 21
3-3 試片的製備及實驗條件 22
3-3-1 M-X非線性外插法求取平衡熔點 22
3-3-2 球晶成長觀察及區型轉移溫度分析 23
3-3-3 熔解熱(△Hu) 23
3-4 實驗流程圖 25
第四章 結果與討論 26
4-1 91.1% PTT/8.9% PET共聚酯之非線性平衡熔點 26
4-2 91.1% PTT/8.9% PET共聚酯之球晶成長速率及等溫結晶Hoffman區型理論分析 28
4-3 91.1% PTT/8.9% PET共聚酯之結晶形態觀察 30
4-4 66.3% PTT/33.7% PET共聚酯之非線性平衡熔點 31
4-5 66.3% PTT/33.7% PET共聚酯之球晶成長速率及等溫結晶Hoffman區型理論分析 35
4-6 66.3% PTT/33.7% PET共聚酯之結晶形態觀察 37
4-7 62.1% PTT/37.9% PET共聚酯之非線性平衡熔點 38
4-8 62.1% PTT/37.9% PET共聚酯之球晶成長速率及等溫結晶Hoffman區型理論分析 40
4-9 62.1% PTT/37.9% PET共聚酯之結晶形態觀察 42
4-10 Regime Ⅰ→Ⅱ轉移溫度分析 43
4-11 66.3% PTT/33.7% PET共聚酯之熔解熱(△Hu) 45
4-12 62.1% PTT/37.9% PET共聚酯之熔解熱(△Hu) 46
第五章 結論 49
第六章 參考文獻 51

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