聚對苯二甲酸乙二酯/己二酸/聚乙二醇(0.009莫耳比)三組份共聚合體物性之研究

Investigation on the physical properties of PET/AA/PEG (0.009 mole ratio) Tri-component Copolymer

彭貞如(Jhen-Ru Peng)

指導教授 ： 芮祥鵬

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2012年)

摘要

實驗的方法為合成聚對苯二甲酸乙二酯(Polyethylene terephthalate , PET)過程中添加0 mole ratio (AA-1)、0.037 mole ratio (AA-2)、0.075 mole ratio (AA-3)、0.117 mole ratio (AA-4)的己二酸(Adipic acid , AA)以及固定量為0.009 mole ratio的聚乙二醇(polyethylene glycol , PEG)成分，而製做出三組份共聚合物，進行物性分析探討。
首先以NMR圖譜分析證明於PET結構中有接上PEG、AA鏈段；以GPC分析得到PDI值介於4~6之間；以DSC、DMA測得Tm、Tg及機械性質測試結果，都是隨著AA添加量變多而下降，以TGA測得Td都落在同一溫度區間；使用XRD測得結晶度與DSC (Tc)有相同趨勢性，於AA-1因只添加PEG而造成分子團聚，結晶度因而上升，但添加入AA，使得結晶度隨添加量變多下降。
再使用流變儀，進而分析黏彈性質，其G'、G"會隨著溫度升高以及AA添加量變多有降低趨勢，測得所有行為模式都是似液狀(liquid-like)，於頻率10 rad/s時，計算270°與250°間之G'差值，可得到隨著AA添加量越多，G'差值越小。並以cole cole plot測試探討其相容性，證明PEG、AA與PET於融熔態不相容材料。
最後使用DSC進行等溫結晶分析，由Avrami方程式運算，得到n值、k值與DSC Tc和DSC結晶度與XRD結晶度為相同結果。再從半結晶時間(t1/2)、結晶速率(G1/2)得知，等溫結晶溫度越高，使得t1/2越短，G1/2越快。PET/PEG/AA 三組份共聚合物屬於均相成核的機制成長。

關鍵字

聚對苯二甲酸乙二酯 ； 己二酸 ； 聚乙二醇 ； cole-cole plot ； 流變性質

並列摘要

The aim to this study is to analysis tri-component copolymers of PET (Polyethylene Terephthalate). We added different percentage of AA (Adipic Acid) – 0 mole ratio (AA-1), 0.037 mole ratio (AA-2), 0.075 mole ratio (AA-3), and 0.117 mole ratio (AA-4) together with fixed amount of 0.009 mole ratio PEG (Polyethylene Glycol) to synthesis PET. To investigate their physical properties, we done series of tests on these tri-component copolymers.

Firstly we analysis from NMR spectrum and proved that the PET structures had grafted with PEG and AA. With GPC analysis, we known that PDI value is between 4 to 6. Using DSC and DMA to determine their Tm point, Tg point, and mechanical properties. We had found that by increasing AA percentage in the copolymer, their results were decreasing. By TGA, we had figured out the Td points were in the same temperature zone. We evaluated crystallinity with XRD, and we found that they had same direction with DSC (Tc). In AA-1 copolymer, we only added PEG and crystallinity was increased. By addition of AA, the crystallinity decreased.

Then, we analyses viscoelastic properties by Rheometer. The G’ and G” was decreased by the increase of temperature and AA additon. All the results were liquid-like behavior. During frequency of 10 rad/s, we evaluated difference of G’ value between 270° and 250°. We had found out with increasing of AA addition, the difference of G’ value were decreased. Furthermore, we used cole-cole plot method to test their compatibility. We had proved that PEG, AA, and PEG were incompatible materials.

Finally we used DSC to analysis isothermal crystallization. Operating by Avrami equation, we had ploted n value, k value and Tc point in DSC. The crystallization of DSC had same results with crystallization of XRD. From the result of half-time crystallization (t1/2) and crystallization rate (G1/2), we had known that by the increase of isothermal crystallization temperature, the t1/2 value decreased and the G1/2 value increased. The mechanism of PET/PEG/AA tri-component copolymers is a homogeneous nucleation.

並列關鍵字

Polyethylene terephthalate ； Adipic Acid ； Polyethylene Glycol ； cole-cole plot ； Rheology

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