臺灣博碩士論文加值系統

聚對苯二甲酸乙二酯(PET)是一種重要的熱塑性聚酯，由於近年對於環境問題的日益關注，廢棄物處理已成為一個重要的社會問題，PET的回收似乎是最理想的廢棄物處理方法，然而經過重複熱處理的PET材料可能發生熱裂解造成材料性能降低的問題，故本研究利用原子轉移自由基聚合(ATRP)合成雙親性嵌段共聚高分子進行處理，改善回收品性質，期望能使回收PET維持原本的物理性質，而黏度及機械性質則有明顯提升，材料選擇為單體2-Hydroxyethyl methacrylate (HEMA)及Glycidyl methacrylate (GMA)。首先，將HEMA單體利用ATRP法先備製出大分子引發劑Poly(HEMA)-Br作為雙鏈共聚物之第一鏈段，隨後第二鏈段GMA的團塊聚合以大分子引發劑Poly(HEMA)-Br作為基底，利用ATRP的方式將單體GMA做嵌段聚合並接合在Poly(HEMA)-Br上，合成出雙嵌段共聚物Poly(HEMA)-b-Poly(GMA)，接著將合成後的聚合物進行1H-NMR基礎性質鑑定及凝膠滲透層析儀(GPC)分析分子量及其分佈。主要利用鏈延長的功能性化合物與PET端基反應，使得在加工和使用過程中破裂的聚合物鏈可以重新結合，從而使聚合物分子具有更高的分子量和改進的性質，達到改善回收PET性質的目的。再將其利用微型雙螺桿成功做出各種比例的共聚物，透過奧士華黏度計、拉伸機等測試可得到優良的機械性質。預計未來在環保回收PET之應用(如:環保紗、包裝材和照相膠片)上將大放異彩。

Polyethylene terephthalate (PET) is an important thermoplastic polyester. Due to the increasing attention to environmental issues in recent years, waste disposal has become an important social issue. PET recycling seems to be an ideal waste treatment. However, the repeated heat treatment of PET materials may cause reduced properties due to thermal degradation. In this study, amphiphilic block copolymer macromolecules were synthesized by atom transfer radical polymerization (ATRP) to improve the properties of the recycled products. It is expected that the recycled PET maintain its original physical properties, while the viscosity and mechanical properties are significantly improved. The materials selected were monomers 2-Hydroxyethyl methacrylate (HEMA) and Glycidyl methacrylate (GMA). The macroinitiator poly(HEMA)-Br was prepared as the first segment of the diblock copolymer by using ATRP as the HEMA monomer, followed by, the second segment that was based on the macroinitiator Poly(HEMA)-Br which was bonded with GMA monomer by ATRP. The synthesized diblock copolymer Poly(HEMA)-b-Poly(GMA) was then subjected to 1H-NMR characterization and gel permeation chromatography (GPC) for analysis of molecular weight and its distribution. The main goal is to use of chain extension functional compounds and PET end-group reaction, so that in the process of processing and use of broken polymer chain can be re-combined, in order that polymer molecules have higher molecular weight and improved properties, to improve the recycled PET properties. The use of twin screw extruder to successfully make a variety of copolymers, its through the Ostwald Viscometer, SS curves can obtain excellent mechanical properties. It is expected to make a splash in future applications for environmentally friendly recycling of PET, such as eco-friendly yarn, packaging materials and photographic film.

摘要 i
Abstract ii
誌謝 iv
目錄 v
圖目錄 viii
表目錄 x
第一章 緒論 1
1.1前言 1
1.2研究動機 2
第二章 文獻回顧 4
2.1原子轉移自由基聚合原理 4
2.1.1可控/活性自由基聚合概述 4
2.1.2原子轉移自由基聚合反應機制 5
2.1.3反應條件控制 6
2.1.4高分子設計 8
2.2高分子混摻應用原理 10
2.2.1摻合物種類 10
2.2.2高分子聚摻合的方法 11
2.3聚對苯二甲酸乙二酯(Polyethylene terephthalate，PET)介紹及其應用 12
2.3.1 PET回收處理現況 13
2.3.2不同用途的PET特性比較 14
第三章 實驗步驟 15
3.1 實驗材料 15
3.2實驗設備 16
3.3 實驗流程 16
3.3.1通過ATRP以一鍋製程製備雙嵌段共聚物 16
3.3.2PHEMA-b-PGMA於高分子的混摻應用 17
3.3.3實驗流程圖 17
3.4測試與分析儀器 18
3.4.1核磁共振光譜分析儀(NMR) 18
3.4.2凝膠滲透層析儀(GPC) 18
3.4.3微型雙螺桿混摻機 18
3.4.4動態機械分析(DMA) 19
3.4.5示差掃描量熱儀(DSC) 19
3.4.6熱重量分析儀(TGA) 19
3.4.7奧士華黏度計 20
3.4.8萬能拉力試驗機 20
第四章 結果與討論 21
4.1合成雙親性嵌段共聚物之探討 21
4.1.1通過ATRP以一鍋法合成雙嵌段共聚物 21
4.1.2 NMR圖譜分析 22
4.2嵌段共聚物的熱性質探討 28
4.2.1 TGA 28
4.2.2 DSC 29
4.3嵌段共聚物應用於高分子回收PET混摻之熱性質探討 31
4.3.1 TGA 31
4.3.2 DSC 35
4.3.3 DMA 42
4.4嵌段共聚物應用於高分子回收PET混摻之黏度探討 50
4.5嵌段共聚物應用於高分子回收PET混摻之機械性質探討 52
4.5.1 萬能拉力試驗機 52
第五章 結論 57
參考文獻 58

 

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