研究生: |
蕭耀貴 Yao-Kuei Hsiao |
---|---|
論文名稱: |
聚對苯二甲酸乙二酯聚摻合改質研究 Studies on Polymer Blend Modification of Polyethylene Terephthalate |
指導教授: |
邱顯堂
Hsien-Tang Chiu |
口試委員: |
邱士軒
Shih-Hsuan Chiu 李俊毅 Jiunn-Yih Lee |
學位類別: |
博士 Doctor |
系所名稱: |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
論文出版年: | 2006 |
畢業學年度: | 94 |
語文別: | 中文 |
論文頁數: | 95 |
中文關鍵詞: | PET 、POE 、HDPE 、PP 、彈性體 、韌性 、相容化劑 |
外文關鍵詞: | PET, POE, HDPE, PP, elastomer, toughness, comp |
相關次數: | 點閱:337 下載:23 |
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中文摘要
Polyethylene terephthate(PET)是目前最便宜的工程塑膠,具有相當好的機械性質及物性,但韌性不足為其主要缺點。近10年來,它被大量使用在包裝及容器用途,取代金屬、玻璃紙及其他塑膠材料(如PVC等),根據行政院環保署的統計(詳如表1-1),PET是近10年來,成長最快,也是最大量的廢塑膠容器,Polypropylene(PP)及polyethylene(PE)則排名第二。若以2004年台灣回收的80,358公噸PET保特瓶為例,換算成600cc的礦泉水瓶,約為31億5千萬支瓶子,數量相當驚人。因此,資源再生,回收再利的課題值得省思,由於回收過程中,徹底篩選分離很難百分之百達成,一般而言,難免有少量PE或PP(廢塑膠容器量排名第二)等材質殘留或摻雜其中,而PET屬極性高分子材料,PE及PP均屬非極性高分子材料,互不相容,若混合回收,勢將嚴重影響回收料品質及其附加價值,因此,如何改善PET及PET與PE或PP間之相容性,即是本研究的重要課題。
利用polyethylene-octene elastomer (POE)接枝maleic anhydride(MA)成POE-g-MA共聚合物(copolymer)當相容化劑及耐衝擊改質劑,對PET、PET/HDPE及PET/PP等摻合物(blends)進行摻合加工改質研究,並利用機械性質(mechanical properties)測試分析,傅立葉轉換紅外線光譜鑑定分析(Fourier transform infra-red spectroscopy,FTIR),動態機械性質分析(dynamic mechanical analysis,DMA),形態學(morphology)觀察分析、流變行為(rheological behavior)分析及界面強力(interfacial tension)分析等來研究相容性及韌性等改質效果。
經由上述之研究分析,大致獲得下列幾項重要結果:
1. POE-g-MA為具極性官能基(polar functional group)彈性體(elastomer)因MA與PET中的-OH未端基有很好的交互作用(interaction),可增進POE-g-MA彈性體與PET的相容性。因此,耐衝擊改質效果成效卓越,只要添加20% POE-g-MA,可使PET的缺口Izod衝擊強度(notched Izod impact strength)從30J/m,提升到1000J/m,足足增韌33倍以上,且即使在低溫(0℃,-20℃及-40℃)也具有相當好的增韌效果。POE-g-MA對PET寶特瓶回收料也具同樣優越的增韌改質效果。
2. 從FTIR、掃描式電子顯微鏡(scanning electron microscopy, SEM)及流變行為等研究分析顯示,POE-g-MA可有效地增進PET與HDPE的相容性,在PET基材與HDPE分散相間的界面形成界面接著(interfacial adhesion)現象。衝擊強度測試結果顯示,添加20phr POE-g-MA可提高80PET/20PP摻合物的常溫衝擊強度達31倍之高(從30J/m提高到930J/m),即使在低溫,仍有相當好的增韌改質效果。
3. 從FTIR、SEM、DMA及流變行為等研究分析顯示,POE-g-MA對PET與PP的相容性改善,一樣有顯著的改質效果,也會在PET基材與PP分散相間的界面形成界面接著現象,衝擊強度測試結果顯示,添加20phr POE-g-MA可將80PET/20PP摻合物的常溫衝擊強度從33J/m提昇到789J/m,約提高了24倍的韌性,但由於POE-g-MA為彈性體柔軟的材料特性,致使PET/PP/POE-g-MA摻合物的抗張強度、彎曲強度及彎曲模數等機械性質,均較PET/PP摻合物為低。
4. 比較POE-g-MA對PET/HDPE及PET/PP摻合物的韌性改質效果,添加20phr POE-g-MA可將80PET/20HDPE摻合物的衝擊強度從30J/m提昇到930J/m,而只能將80PET/20PP摻合物的衝擊強度從33J/m提昇到789J/m。顯然,POE-g-MA對PET/HDPE摻合物較具韌性改質效果。
關鍵字:PET、POE、HDPE、PP、彈性體、韌性、相容化劑
ABSTRACT
Polyethylene terephthalate(PET) is the cheapest engineering plastic with excellent mechanical and physical properties at present; however, pool toughness is its weakness. In recent ten years, it is widely used in packaging and containers to replaces metals, and cellophane, and the other plastics(e.g PVC). Regarding the statistics from Environmental Protection Administration(see table 1-1).PET is the fastest growing and the greatest number of waste plastic containers in the last ten years. Polypropylene(PP) and Polyethylene(PE) are No. 2. In 2004, there are 80,358 tons recycled PET bottles in Taiwan. It is equal to 3.15 billion 600cc mineral water bottles.The quantity is alarming. Thus, the subjects of resource “reusing”, “recycling”and “recovering” are very important to us. In the process of recycling, to completely sieve and separate out PE/PP(the second largest quantities of waste plastic containers)is very difficult, so a few might be mixed up with PET. Because PET is polar polymer, but PE and PP are nonpolar polymer materials, they are not compatible. If we recycle them together, it will influence the quality and value added of recycling materials. So, how to improve the compatibility of PET, PET and PE, or PP is the major objective of this research.
Using polyethylene-octene elastomer(POE) to graft maleic anthydride(MA), then it will become POE-g-MA copolymer. It could be compatibilizer and impact modifier to do a blending processing modifying research on blends, like PET, PET/HDPE and PET/PP. Also, use mechanical properties testing analysis, Fourier transform infra-red spectroscopy(FITR), dynamic mechanical analysis(DMA), morphology observation analysis, rheological behavior and interfacial tension analysis to research their modification effects, such as compatibility and toughness
Regarding the analysis above, we got the following important results.
1. POE-g-MA is an elastomer with polar functional group. Because MA is interacting well with –OH of PET, it could improve the compatibility between POE-g-MA and PET. So, the impact strength modification is outstanding. Adding 20% POE-g-MA will increase PET’s notched Izod impact strength from 30 J/m to 1000 J/m. The toughening effect is over 33 times better than before. Even in low temperature(0℃,-20℃, and -40℃), the toughening effect is excellent as well. POE-g-MA also brings nice toughening modification to recycling materials of PET bottle.
2. Regarding the results of FTIR, scanning eclectron microscopy(SEM), and rheological behavior analysis, POE-g-MA could efficiently improve the compatibility between PET and HDPE, and we find interfacial adhesion between the faces of PET substrate and HDPE dispersed phase. The result of impact strength test show adding 30 phr POE-g-MA will increase 80PET/20PP blends’ room temperature impact strength 31 times (from 30 J/m to 930 J/m). Even in low temperature, toughness modification is still outstanding.
3. FTIR, SEM, DMA and rheological behavior analysis reveal better compatibility between PET and PP brings better modification effect. And interfacial adhesion is also found between the faces of PET substrate and PP dispersed phase. Impact strength test result shows adding 20 phr POE-g-MA will increase 80 PET/20PP blends’ room temperature impact strength 24 times(from 33 J/m to 789 J/m). Due to the material specialty that POE-g-MA is a soft elastomer, PET/PP/POE-g-MA blends’ mechanical properties, such as tensile strength, flexural strength and flexural modulus, are weaker than PET/PP blends’.
4. To compare the toughness modification effects that POE-g-MA acts on PET/HDPE and PET/PP blends, adding 20 phr POE-g-MA would increase 80PET/20HDPE blends’ impact strength from 30J/m to 930 J/m, but increase 80PET/20PP blends’ impact strength from 33J/m to 789J/m only. Obviously, POE-g-MA provides better toughening modification effect on PET/HDPE blends.
Keywords:PET、POE、 HDPE、 PP、elastomer、toughness、compatibilizer
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