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研究生： 陳子權
Chen, Tzu-Chuan
論文名稱： 利用多元醇對PET回收料進行酯交換並應用於超臨界氮氣發泡之研究
Modifying recycling PET Bottles by transesterfication using polyol for supercritical N2 foaming
指導教授： 陳炳宏
Chen, Bing-Hong
共同指導: 陳志勇
Chen, Chuh-Yung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2023
畢業學年度： 111
語文別： 中文
論文頁數： 69
中文關鍵詞： 熔融聚合法 、多嵌段改質PET 、化學回收 、物理發泡
外文關鍵詞： melt polymerization, modified block copolymerized PET, chemical recycle, physical foaming
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    • 本研究透過化學混摻的方式將聚對苯二甲酸乙二酯(PET)與不同比例之1,4-丁二醇(1,4-BDO)、2-甲基-1,3-丙二醇(MPO)以及聚四氫呋喃(PTMEG)進行酯交換反應，並且探討在不同反應溫度下酯交換轉化率對聚酯性質的影響，以提升回收PET的性質並將其運用於物理發泡中。研究結果顯示，降低酯交換反應溫度會使1,4-BDO轉化率從80%上升為87%，進而提高1,4-BDO的占比，使得產品本質黏度(IV)從上升至1.33、熔點下降為147 ℃以及物性下降；添加1,4-BDO鏈段可明顯增加 rPET 改質後的柔軟度至硬度30D及彈力44 %，並降低材料的熔點137 ℃以及延伸率689 %和斷裂應力 163 kgf/cm2；添加PTMEG 鏈段可觀察到rPET硬度變為25D、彈力上升至52 %及延伸率提升為774%，斷裂應力則下降為132 kgf/cm2¬，經 DSC分析後發現熔點下降為126 ℃，由於分子鏈段較長，影響程度較1,4-BDO大。添加MPO鏈段後的樣本經DSC加熱曲線分析顯示，改質後的PET會因為其側鏈甲基基團的導入而明顯降低 PET 的冷結晶放熱7.1 J/g為以及熔融吸熱為6.2 J/g。後續針對改質後的PET與擴鏈劑Poly(styrene-co-glycidyl methacrylate) (PSG)一同進行混摻，混摻物經硫變儀量測結果顯示，混摻物的熔融黏度提升顯示PSG對改質PET具有擴鏈的效果。另在發泡製程中發現，添加2 phr的PSG材料熔融強度足以支撐發泡材，製備出來的泡材各項物性數值皆優於市面上常見之EVA發泡材特別是在回彈力為58%、抗撕裂4.8 kgf/cm2¬以及永久壓縮率為34%，顯示本研究所開發的PET的化學回收為PET回收產業鏈提供了創新並且更廣泛應用前景。

    In this experiment, we investigated the synthesis and properties of Thermoplastic Polyester Elastomer (TPEE) obtained through transesterification and condensation reactions involving recycled PET bottles and polyols. First, we optimized reaction conditions for achieving improved grafting efficiency and material performance. By varying reaction temperatures and degree of polycondensation, we identified that low temperature reactions and high degree of polycondensation favored enhanced grafting rates and desirable material characteristics. Second, we explored the impact of different polyol proportions on the properties of TPEE. As the proportion of polyols increased, the intrinsic viscosity (IV) significantly rose. Notably, an increase in 1,4-BDO proportion contributed to a reduction in the melting point, albeit with a decline in material properties. Similarly, a higher proportion of MPO led to a remarkable decrease in crystallization and melting enthalpies, adversely affecting material properties. Conversely, an increase in PTMEG proportion exhibited a substantial enhancement in resilience and elongation , despite a decrease in material strength. Third, In terms of post-processing, we successfully achieved chain extension reactions by incorporating TPEE with the chain extender PSG (Poly(styrene-co-glycidyl methacrylate)). The addition of 2phr PSG enabled successful supercritical physical foaming, leading to superior resilience and compression deformation performance compared to commonly used EVA foam materials available in the market. The results from this comprehensive study provide valuable insights into the synthesis and properties of TPEE, offering potential applications in various industries, particularly as an ecofriendly alternative to conventional materials.

    中文摘要 I RESULTS AND DISCUSSION V 總目錄 XXVIII 圖目錄 XXXI 表目錄 XXXIII 第一章 緒論 1 第二章 文獻回顧 5 2-1.聚對苯二甲酸乙二醇酯(PET) 5 2-2.回收PET 6 2-1-1 PET廢物的物理回收 7 2-1-2 PET廢棄物的化學回收 7 2-3酯化觸媒 11 2-3-1金屬催化劑 12 2-3-2水滑石(Layered double hydroxides) 12 2-4化學混摻 15 2-4-1 PBT型及PTT型多嵌段共聚物 16 2-4-2多嵌段共聚物可加工性 16 2-5高分子發泡材 17 2-5-1高分子發泡的類別以及應用 17 2-5-2發泡製程 17 2-6 PET熔融改質技術 19 第三章 實驗步驟 22 3-1實驗藥品 22 3-2實驗儀器 22 3-3實驗步驟 23 3-3-1 高壓反應器操作步驟(PET化學改質) 23 3-3-2 LDH-S之製備 25 3-3-3 mPET 發泡試片製作 25 3-3-3 超臨界N2含浸發泡 25 3-3-4 實驗分析方法 26 第四章 結果與討論 30 4-1化學改質回收 PET 瓶片(rPET) 30 4-2酯交換溫度對多元醇改質 rPET影響 36 4-2-1酯交換溫度對多元醇改質 rPET結構鑑定 36 4-2-2酯交換溫度對多元醇改質 rPET熱性質鑑定 37 4-2-3酯交換溫度對多元醇改質 rPET強度測試 39 4-3酯交換縮聚程度對多元醇改質 rPET影響 40 4-3-1酯交換縮聚程度對多元醇改質 rPET結構鑑定 40 4-3-2不同IV值對多元醇改質 rPET熱性質鑑定 41 4-3-3不同IV值對多元醇改質 rPET強度測試 43 4-4多元醇改質 rPET 44 4-4-1多元醇改質 rPET結構鑑定 45 4-4-2多元醇改質 rPET熱性質鑑定 46 4-4-3多元醇改質 rPET強度測試 52 4-5改質 rPET與PSG反應性探討 57 4-6改質 rPET發泡材之物性分析 58 4-6-1高熔點配方發泡 58 4-6-2低熔點配方發泡 60 4-6-3市售發泡產品比較 62 第五章 結論 64 第六章 參考文獻 65

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