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研究生:王彥博
研究生(外文):Yen-Po Wang
論文名稱:液晶共聚酯與聚對苯二甲酸丙酯摻合物之結晶性質研究
論文名稱(外文):Crystallization in Blend of Liquid Crystalline Copolyester and Poly(trimethylene terephthalate)
指導教授:韋 光 華
指導教授(外文):Kung-Hwa Wei
學位類別:碩士
校院名稱:國立交通大學
系所名稱:材料科學與工程系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:80
中文關鍵詞:聚對苯二甲酸丙酯結晶性質液晶共聚酯摻合物液晶共聚酯
外文關鍵詞:Poly(trimethylene terephthalate)Liquid Crystalline Copolyesterisothermal and non-isothermal crystallizationcoherecn lengthAvrami equationOzawa equationPTT
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本碩士論文為研究液晶高分子與工程塑膠(PTT)的摻合,製成高分子複合材料,探討其相容性、結晶性質與酯交換反應的研究。
利用DSC研究雜式液晶共聚酯copoly (oxybenzoate-terephthalate)莫爾分率為60/40的P64與聚對苯二甲酸丙酯poly(trimethylene terephthalate)(PTT)摻合物之相容性。我們可以發現P64/PTT摻合物無定型區域,其分子間的作用力為中等,而由熔點下降分析所獲得的Flory-Huggins interaction parameter為-0.17,顯示在熱熔態時摻合物中的P64與PTT為相容的。而由偏光顯微鏡(POM)的研究,當PTT含量有5wt%的P64時,呈現出最大的晶體。再由廣角X-ray的繞射圖譜分析中得知,經計算其Miller , 及 面的coherence length值在加入5wt%的P64時為最大,表示少量的P64對於PTT分子鏈的排列更為有規則(regularity),結晶變得更大,這與POM所觀察出的結果一致。
在PTT及P64/PTT摻合物之等溫結晶動力學(Isothermal crystallization kinetics)的研究中,在Avrami plot中摻合物呈現出一次和二次結晶的行為,經分析一次結晶之Avrami exponent,可得知隨著P64的含量增加而下降,顯示出球晶成長方式的改變;而結晶速率常數值,隨著P64/PTT摻合物中的P64含量增加而下降,原因為P64含量增加會破壞PTT結晶的對稱性(symmetry),使結晶速率變小。而非等溫結晶動力學(Non-isothermal crystallization kinetics)的研究中,由於P64/PTT摻合物存在著二次結晶的現象,使得一般常用的Ozawa equation無法適用,因此我們選用另一種結合了Avrami和Ozawa的方程式來模擬,其結果與等溫結晶動力學一致。故由熱分析的結果顯示P64/PTT摻合物具有一定程度的相容性。
由於P64/PTT摻合物在高溫下,可能會有酯交換反應發生,而影響到摻合物之物性,因此我們利用13C和1H 核磁共振光譜儀來判斷雜式液晶共聚酯P64與對苯二甲酸丙酯PTT的摻合物,是否發生酯交換反應。我們可以發現在300℃持溫30 分鐘都沒有酯交換反應發生,因此可知在我們實驗過程當中所進行的持溫程序並不會發生酯交換反應而影響到結果。

The miscibility and the crystallization kinetics in blends of random liquid crystalline copoly(oxybenzoate -ethylene terephthalate) at molar ratio 60/40 (P64) and semicrystalline poly(trimethylene terephthalate) (PTT) were investigated with differential scanning calorimetry, wide angle X-ray diffraction and polarized optical micrography. It was found that P64 and PTT were partially miscible as evidenced from the appearance of molecular interaction force close to middle in amorphous region. Furthermore, the Flory-Huggins interaction parameter, 12, for P64 and PTT was determined to be — 0.17 through the melting point depression analysis, indicating miscibility in blends of P64 and PTT at the melt state. The coherence lengths of PTT in the presence of a small amount (around 5 wt%) of P64 were larger than that in pure PTT.
The isothermal and non-isothermal crystallization behavior in blends of P64 and PTT were studied with differential scanning calorimetry. In isothermal crystallization experiment, the PTT crystallization temperature, Avrami exponent and the crystallization rate coefficient had were found to decrease with increase the concentrate of P64 . In non-isothermal crystallization experiment, we found that the Ozawa equation can not work on our case. We selected another one equation to discuss our results.
The 13C and 1H nuclear magnetic resonance was not found that the ester exchange in the two polymers take place within 30 min when the blend was annealed at 300oC.

中文摘要 i
英文摘要 iii
誌謝 v
目錄 vi
表目錄 viii
圖目錄 viii
一、緒論 1
1-1引言 1
1-2液晶共聚酯簡介 2
1-3聚對苯二甲酸丙酯高分子簡介 6
1-4高分子摻合物相容性之探討 7
1-5高分子摻合物之結晶動力學 10
1-6聚酯高分子摻合物之酯交換反應 13
1-7研究動機及目的 14
二、實驗藥品與儀器 15
2-1藥品 15
2-2實驗儀器 16
三、實驗方法 17
3-1溶液摻合 17
3-2熱分析儀(DSC) 分析 17
3-3摻合物的平衡熔點(Tmo)之量測 18
3-4偏光顯微鏡(POM) 18
3-5廣角X-Ray繞射 19
3-6等溫結晶動力學(Isothermal crystallization kinetics) 19
3-7非等溫結晶動力學(Non-isothermal crystallization kinetics) 19
3-8核磁共振實驗樣品之製備 20
四、結果與討論 21
4-1相容性分析 21
4-1-1摻合物無定型區域相容性之探討 21
4-1-2摻合物的平衡熔點(Tmo)以及Flory-Huggins作用參數 22
4-2摻合物形態分析 26
4-2-1摻合物之偏光顯微鏡分析 26
4-2-2摻合物之X-Ray繞射圖譜分析 27
4-3結晶動力學分析 30
4-3-1摻合物等溫結晶動力學 30
4-3-2摻合物非等溫結晶動力學 32
4-4酯交換反應分析 37
4-4-1摻合物酯交換反應 37
五、總結 39
六、參考文獻 40

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