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系統識別號 U0002-0808200809315300
中文論文名稱 聚丙烯/玉米澱粉崩解性複合材料之製備及性質之研究
英文論文名稱 A Study on the Preparation and Properties of the Polypropylene/Corn Starch Destructible Polymer Composites
校院名稱 淡江大學
系所名稱(中) 化學工程與材料工程學系碩士班
系所名稱(英) Department of Chemical and Materials Engineering
學年度 96
學期 2
出版年 97
研究生中文姓名 林育新
研究生英文姓名 Yu- Hsin Lin
學號 695401348
學位類別 碩士
語文別 中文
口試日期 2008-07-22
論文頁數 124頁
口試委員 指導教授-林國賡
委員-賴森茂
委員-董崇民
中文關鍵字 聚丙烯  澱粉  崩解性複合材料  糊化  馬來酸酐  熔融混煉  流變性質 
英文關鍵字 Polypropylene  Corn starch  Destructible Polymer Composites  Maleic anhydride  Melt mixing  Rheology 
學科別分類
中文摘要 本研究主要以聚丙烯(PP)與玉米澱粉之熔融混煉製成崩解性複合材料。以添加不同接枝率之馬來酸酐相容劑(PP-g-MA或PB3200)及改質澱粉於PP基材中,進行各種性質分析。極性澱粉與非極性PP可由SEM、TGA及DSC觀察兩者不相容之情形。且隨著澱粉增加,因為嚴重相分離及低分子量之相容劑添加過量,使得機械性質下降。
未添加相容劑之複材與摻混0.5phr PP-g-MA之複材中,仍有大顆粒玉米澱粉存在,其餘配方經混煉過程之強大剪切力,及相容劑附著,撕裂成細碎小顆粒。
藉由FTIR可發現相容劑與澱粉(未糊化)之羥基(-OH)並無化學接枝反應,而是以物理作用力(Van der Waal force或hydrogen bonding)提升複材之相容性及機械性質。流變性質測試中,可發現複材之儲存模數(G´),會隨著添加相容劑之相容作用而上升。由動態機械與拉伸測試分析結果,發現相容劑PB3200添加5phr是不足的,而PP-g-MA最佳值為1phr。且由於相容劑接枝率及其分子量上的差異,本研究發現添加相容劑PB3200複材之機械性質較添加相容劑PP-g-MA略差。
英文摘要 In this study, we aim at blending polypropylene/corn starch by melt-
mixing to manufacture destructible polymer composites. We compounded
polypropylene with various concentrations of compatiblizer and modified corn starch by a Brabender mixer. Then, the different properties of destructible polymer composites were analyzed.
The high levels of immiscibility in the polar-nonpolar corn starch-PP system were shown by SEM, DSC, and TGA. Serious phase separation and/or excess compatiblizer added may cause bad mechanical properties. The results of SEM showed that polymer composites with compatiblizers added below 0.5 phr had great starch granules. Moreover, the corn starch might be cut to small bits by great shear stress and adherent compatiblizers during melt-mixing process, if the content of compatibilizer was over 0.5 phr. The FTIR spectra showed that maleic anhydride groups had no chemical graft reaction with the hydroxyl groups in the unmodified corn starch.
Appropriate amount of compatibilizer added may cause an improvement for the mechanical properties of polymer composites, due to the physical intermolecular force (Van der Waal force or hydrogen bonding) between the maleic anhydride and corn starch. The results of rheological analysis showed that the storage modulus went up because of the compatibilizing effect.
We could observe that the amount of PB3200 added up to 5 phr is insufficient to improve the mechanical properties of polymer composites. The suitable concentration of compatiblizer (PP-g-MA) was 1phr. We concluded in this study, based on the different grafting ratios and molecular weight that the mechanical properties of polymer composites with PB3200 were lower than with PP-g-MA .
論文目次 總目錄
致謝 I
中文摘要 II
英文摘要 III
總目錄 IV
圖目錄 VI
表目錄 IX
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 3
第二章 文獻回顧 6
2.1 分解性塑膠種類 6
2.1.1 崩解性塑膠填充材之種類 7
2.2澱粉之簡介 7
2.2.1 澱粉之物理結構與性質 7
2.2.2 常見澱粉[54] 10
2.3 混合及摻合方式 14
2.4 相容劑種類 15
2.5 崩解性複材文獻回顧 19
第三章 理論基礎 23
3.1 生物分解性 23
3.2 填充複合材料 27
3.3 填充複合材料之相容性 28
3.4 流變學原理 30
3.4.1 流變學研究內容與意義 30
3.4.2 剪切黏度 31
3.4.3 動態流變行為 33
3.4.4 線性黏彈性質 34
3.5 抗張測試[46] 35
第四章 實驗 37
4.1 實驗材料 37
4.2 實驗儀器 39
4.3 實驗方法 43
4.3.1 PP1080/玉米澱粉之製備 43
4.3.2 PP1080/玉米澱粉/PP-g-MA之複合材料製備 45
4.3.3 PP1080/玉米澱粉/PB3200之複合材料製備 47
4.3.4 PP1080/改質玉米澱粉之複合材料製備 49
4.4 材料測試與分析 51
4.5 樣品分析流程 54
第五章 結果與討論 55
5.1 SEM微觀相形態 55
5.2 紅外線光譜(FTIR) 68
5.3 DSC熱分析探討 73
5.4 TGA熱重損失分析 82
5.5 流變分析 94
5.6 動態機械分析(DMA) 100
5.7 拉伸測試分析 107
第六章 結論 115
第七章 參考文獻 117
圖目錄

圖2-1 直鏈澱粉化學結構 8
圖2-2 支鏈澱粉化學結構 9
圖2-3 玉米澱粉SEM圖 10
圖2-4 各種化學澱粉分類[54] 13
圖2-5 相容劑種類 16
圖3-1 生物可分解塑膠的檢測、標準與認證 26
圖3-2 純張力 36
圖4-1 聚丙烯/玉米澱粉 複合材料的製備流程圖 44
圖4-2 PP1080/玉米澱粉/PP-g-MA複合材料的製備流程圖 46
圖4-2 PP1080/玉米澱粉/PB3200複合材料的製備流程圖 48
圖4-3 PP1080/PP-g-MA /玉米澱粉複合材料的製備流程圖 50
圖4-4 PP/玉米澱粉崩解性複材樣品分析流程 54
圖5-1 配方c10之SEM圖(X100) 56
圖5-2 配方c20之SEM圖(X100) 56
圖5-3 配方c30之SEM圖(X100) 57
圖5-4 配方c10之SEM圖(X1000) 57
圖5-5 配方c20之SEM圖(X1000) 58
圖5-6 配方c30之SEM圖(X1000) 58
圖5-7 配方c10m05之SEM圖(X1000) 59
圖5-8 配方c10m1之SEM圖(X1000) 59
圖5-9 配方c10m5之SEM圖(X1000) 60
圖5-10 配方c20m05之SEM圖(X1000) 60
圖5-11 配方c20m1之SEM圖(X1000) 61
圖5-12 配方c20m5之SEM圖(X1000) 61
圖5-13 配方c30m05之SEM圖(X1000) 62
圖5-14 配方c30m1之SEM圖(X1000) 62
圖5-15 配方c30m5之SEM圖(X1000) 63
圖5-16 配方c10pb05 SEM圖 (x1000) 64
圖5-17 配方c10pb1 SEM圖 (x1000) 64
圖5-18 配方c10pb5 SEM圖 (x1000) 65
圖5-19 配方c20pb05 SEM圖 (x1000) 65
圖5-20 配方c20pb1 SEM圖 (x1000) 66
圖5-21 配方c20pb5 SEM圖 (x1000) 66
圖5-22 配方c30pb05 SEM圖 (x1000) 67
圖5-23 配方c30pb1 SEM圖 (x1000) 67
圖5-24 配方c30pb5 SEM圖 (x1000) 68
圖5-25 相容劑PP-g-MA水合之反應機制圖 69
圖5-26 PP-g-MA室溫下與真空80℃之FTIR圖(範圍:4000-400cm-1) 70
圖5-27 PP-g-MA室溫下與真空80℃之FTIR圖(範圍:2000-1000cm-1) 70
圖5-28 相容劑與玉米澱粉之反應機制圖 71
圖5-29 糊化及未糊化玉米澱粉摻混相容劑之FTIR圖(範圍:4000-400cm-1) 72
圖5-30 糊化及未糊化玉米澱粉摻混相容劑之FTIR圖(範圍:2000-1000cm-1) 72
圖5-31 c10添加不同比例相容劑(PP-g-MA)之DSC圖 75
圖5-32 c20添加不同比例相容劑(PP-g-MA)之DSC圖 76
圖5-33 c30添加不同比例相容劑(PP-g-MA)之DSC圖 76
圖5-34 c10添加不同比例相容劑(PB3200)之DSC圖 77
圖5-35 c20添加不同比例相容劑(PB3200)之DSC圖 77
圖5-36 c30添加不同比例相容劑(PB3200)之DSC圖 78
圖5-37 c10添加不同比例相容劑(PP-g-MA)之結晶溫度圖 78
圖5-38 c20添加不同比例相容劑(PP-g-MA)之結晶溫度圖 79
圖5-39 c30添加不同比例相容劑(PP-g-MA)之結晶溫度圖 79
圖5-40 c10添加不同比例相容劑(PB3200)之結晶溫度圖 80
圖5-41 c20添加不同比例相容劑(PB3200)之結晶溫度圖 80
圖5-42 c30添加不同比例相容劑(PB3200)之結晶溫度圖 81
圖5-43 不同比例玉米澱粉之比較圖 84
圖5-44 c10不同PP-g-MA比例之熱重損失圖 84
圖5-45 c20不同PP-g-MA比例之熱重損失圖 85
圖5-46 c30不同PP-g-MA比例之熱重損失圖 85
圖5-47 c10不同PB3200比例之熱重損失圖 86
圖5-48 c20不同PB3200比例之熱重損失圖 86
圖5-49 c30不同PB3200比例之熱重損失圖 87
圖5-50 不同比例玉米澱粉之熱重一階微分圖 87
圖5-51 c10不同PP-g-MA比例之熱重一階微分圖 88
圖5-52 c20不同PP-g-MA比例之熱重一階微分圖 88
圖5-53 c30不同PP-g-MA比例之熱重一階微分圖 89
圖5-54 c10不同PB3200比例之熱重一階微分圖 89
圖5-55 c20不同PB3200比例之熱重一階微分圖 90
圖5-56 c30不同PB3200比例之熱重一階微分圖 90
圖5-57 不同比例澱粉0.5phr PP-g-MA比例之熱重一階微分圖 91
圖5-58 不同比例澱粉1phr PP-g-MA比例之熱重一階微分圖 91
圖5-59 不同比例澱粉5phr PP-g-MA比例之熱重一階微分圖 92
圖5-60 不同比例澱粉0.5phr PB3200比例之熱重一階微分圖 92
圖5-61 不同比例澱粉1phr PB3200比例之熱重一階微分圖 93
圖5-62 不同比例澱粉5phr PB3200比例之熱重一階微分圖 93
圖5-63 不同澱粉比例振幅掃描比較圖 95
圖5-64 不同澱粉比例比較圖 96
圖5-65 c10不同相容劑PP-g-MA比例頻率掃描圖 96
圖5-66 c20不同相容劑PP-g-MA比例頻率掃描圖 97
圖5-67 c30不同相容劑PP-g-MA比例頻率掃描圖 97
圖5-68 c10不同相容劑PB3200比例頻率掃描圖 98
圖5-69 c20不同相容劑PB3200比例頻率掃描圖 98
圖5-70 c30不同相容劑PB3200比例頻率掃描圖 99
圖5-71 不同澱粉比例之儲存模數圖 101
圖5-72 c10不同相容劑PP-g-MA比例之儲存模數圖 102
圖5-73 c20不同相容劑PP-g-MA比例之儲存模數圖 102
圖5-74 c30不同相容劑PP-g-MA比例之儲存模數圖 103
圖5-75 c10不同相容劑PB3200比例之儲存模數圖 103
圖5-76 c20不同相容劑PB3200比例之儲存模數圖 104
圖5-77 c30不同相容劑PB3200比例之儲存模數圖 104
圖5-78 c10不同相容劑比例之之儲存模數圖 105
圖5-79 c20不同相容劑比例之之儲存模數圖 105
圖5-80 c30不同相容劑比例之儲存模數之儲存模數圖 106
圖5-81 不同澱粉比例之拉伸結果 111
圖5-82 PP-g-MA系列之比較 111
圖5-83 PB3200系列之比較 112
圖5-84 不同相容劑之比較 112
圖5-85 不同澱粉比例之斷裂點結果 113
圖5-86 PP-g-MA系列之斷裂點結果 113
圖5-87 PB3200系列之斷裂點結果 114
圖5-88 不同相容劑之斷裂點結果 114

表目錄

表1-1 分物可分解性塑膠與傳統塑膠性質比較 4
表1-2 生物可分解性塑膠、傳統塑膠及澱粉價格表 5
表1-3 各地區生物可分解產品之產能表 5
表2-1 反應型相容劑 17
表2-2 非反應型相容劑 18
表4-1 玉米澱粉成分 38
表4-2 不同混煉時間配方表 43
表4-3 不同添加量之相容劑PP-g-MA配方 45
表4-4 不同添加量之相容劑PB3200配方 47
表4-5 PP摻混改質玉米澱粉之配方 49
表5-1 MA官能基之紅外吸收特性波數 71
表5-2 PP掺混不同含量的玉米澱粉之熔點、吸熱焓、結晶度 74
表5-3 PP添加相容劑(PP-g-MA)系列之熔點、吸熱焓、結晶度 74
表5-4 PP添加相容劑(PB3200)系列之熔點、吸熱焓、結晶度 75
表5-5 不同比例玉米澱粉及相容劑(PP-g-MA)系列 83
表5-6 不同比例玉米澱粉及相容劑(PB3200)系列 83
表5-7 不同澱粉比例之拉伸結果 108
表5-8 PP-g-MA系列之拉伸結果 109
表5-9 PB3200系列之拉伸結果 109




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