臺灣博碩士論文加值系統

本研究分為兩個部分，第一部份:將環氧擴鏈劑與起始劑混摻添加至回收聚乳酸內，以反應性擠壓方式製備得改質聚乳酸PLAAB塑料，進一步再與成核劑變化混摻比例進行混摻改質，製備得再生PLAABC(以代號Cx說明)塑料。再生塑料在FTIR-ATR光學、DSC熱學、機械性質與X-ray進行分析討論。FTIR-ATR光學結果顯示，屬於PLA末端-OH官能基特徵吸收峰(3658,1045 cm-1)消失不見，進一步在1025 cm-1發現新的特徵吸收峰。環氧擴鏈劑與PLA塑料末端-OH官能基進行反應生成新的醚基結構。DSC熱學性質中發現隨著成核劑含量的增加，再生塑料的結晶速率變快，結晶度變大。機械性質顯示，以成核劑1wt%之再生聚乳酸拉伸強力最大，與回收聚乳酸相較，抗張強力增加32%。耐衝擊強度增加132.6%。第二部份: 將回收聚乳酸、酯類彈性體、相容劑F與藥品G在變化混摻比例下進行聚乳酸增韌改質，增韌改質塑料在FTIR-ATR光學、DSC熱學性質、機械性質、斷面型態性質(SEM)與Optical transparency性質進行分析討論。機械性質結果顯示，斷裂伸長率與純聚乳酸相較提升約6566%。耐衝擊強度顯示，與純聚乳酸相較提升約585%。增韌薄膜因藥品G的添加，透明度下降。在600nm處透明度由回收聚乳酸薄膜的90%下降到54%。回收PLA為帶黃色色光的薄膜，增韌薄膜轉變成帶藍綠色光的薄膜。增韌型聚乳酸塑料易加工吹膜，能應用於農膜、包裝、生技、紡織等相關產業。

The study is divided into two parts,the first part: the chain extender and the epoxy initiator added to the collection in the blending of polylactic acid, was prepared by reactive extrusion methods have modified polylactic acid PLAAB plastic, further changes again with a nucleating agent blending proportion of blending modification, preparation was regenerated PLAABC (Cx explain the code) plastic. Recycled plastic in FTIR-ATR、DSC、 mechanical properties and X-ray analyzed and discussed. FTIR-ATR results optics belonging –OH of PLA terminal functional group characteristic absorption (3658,1045 cm-1) disappeared, Further found that the characteristic absorption peaks in the new 1025 cm-1. Epoxy chain extenders and PLA plastics with terminal-OH functional group reacted to generate a new ether structure. DSC thermal properties were found to increase the content of nucleating agent, recycled plastics crystallization rate becomes faster, the degree of crystallinity increases. Mechanical properties are shown to 1wt% of the nucleating agent of polylactic acid regeneration maximum tensile strength, compared with the recovery of polylactic acid, tensile strength increased by 32%. 132.6% increase in impact strength. Second part: the recovered lactic acid, ester elastomers, compatible agent F with pharmaceutical G with toughening modified polylactic acid mixed in the ratio of the change under doping, toughening modified plastics in FTIR-ATR、 DSC、mechanical properties、SEM and optical transparency discussed. The results showed that the mechanical properties, elongation compared with pure PLA increased by approximately 6566%. Impact strength showed, compared with pure PLA increased by approximately 585%. Toughened film by adding G drugs, reduced transparency. The recovery of transparency at 600nm of 90% polylactic acid film decreased to 54%. Recycling PLA film as a yellowish shade, toughened film into a film with a blue-green shade. Toughened polylactic acid plastic film blowing easy processing, can be used in plastic sheeting、packaging、 biotechnology、 textiles and other related industries.

目 錄
論文摘要 I
ABSTRACT II
誌謝 IV
目錄 V
圖表索引 VIII
第一章 前言 1
第二章 文獻回顧 3
2.1生物分解塑膠定義 3
2.2 生物分解性塑膠之分類 3
2.3 生物分解性規範 7
2.4 聚乳酸(Polylactic acid, PLA) 10
2.4.2 聚乳酸之合成 12
2.4.3 聚乳酸晶體結構 13
2.4.4 結構與性能的關係 15
2.4.4.1 玻璃化轉變溫度 15
2.4.4.2 熔融溫度 16
2.4.5 結晶動力學 17
2.4.6 聚乳酸的應用 22
2.4.7 聚乳酸的未來展望 25
2.5 高分子混摻理論 26
2.6 相容劑 36
第三章 實驗 40
3.1 全降解型回收聚乳酸材料再生改質產品技術開發 40
3.1.1 實驗材料 35
3.1.2再生聚乳酸塑料製備 40
3.1.3 紅外線光譜 (FT-IR)性質分析 40
3.1.4 DSC熱學分析 40
3.1.5 機械性質分析 40
3.1.6 IZOD耐衝擊性質分析 40
3.2 全降解型聚乳酸半透明複合膜技術開發 41
3.2.1 實驗材料 41
3.2.2 實聚乳酸複合膜塑料製備 41
3.2.3 紅外線光譜 (FT-IR)性質分析 41
3.2.4 DSC熱學分析 41
3.2.5 機械性質分析 41
3.2.6 形態性質分析 41
3.2.7 紫外光-可見光光譜儀(UV-VIS)穿透度性質分析 42
3.2.8 CIE Lab色彩強度的量測 42
第四章 結果與討論 43
4.1 全降解型回收聚乳酸材料再生改質產品技術開發
4.1.1 傅立葉紅外光譜(FTIR)分析 43
4.1.2 X光繞射儀分析(XRD) 45
4.1.3 DSC熱學性質分析 46
4.1.3.1 DSC熱學性質分析 46
4.1.3.2 非等溫結晶動力學分析 50
4.1.4 動態機械性質分析(DMA) 62
4.1.5 拉伸強力性質分析 66
4.1.6 耐衝擊性質分析 66
4.1.7結論 68
4.2 全降解型聚乳酸半透明複合膜技術開發
4.2.1 傅立葉紅外光譜(FTIR)分析 69
4.2.1.1 PLA，DxEy，D與E的紅外光譜圖 69
4.2.2 X光繞射儀分析(XRD) 71
4.2.3 DSC熱學性質分析 73
4.2.3.1 基礎塑料的熱學性質分析 73
4.2.3.2 複合膜的熱學性質分析 75
4.2.4 動態機械性質分析(DMA) 84
4.2.5 抗張機械性質分析 90
4.2.5.1 基礎塑料的抗張機械性質分析 90
4.2.5.2 複合膜的抗張機械性質分析 91
4.2.6 耐衝擊性質分析 93
4.2.7 SEM表面型態分析 98
4.2.8 Optical transparency 100
4.2.9結論 102
參考文獻 104
作者簡介 121






圖目錄
圖2 – 1兩種不同形式的乳酸化學結構 10
圖2 – 2均聚物的乳酸構型 10
圖2 – 3聚乳酸化學結構 12
圖2 – 4聚乳酸生物分解與循環圖 12
圖2 – 5聚乳酸的製備方法 13
圖2 – 6 Tg與的Mn(平均分子量)的關係圖 16
圖2 - 7熔化溫度與D-lactate含量關係圖 16
圖2 – 8球晶密度與結晶溫度的關係圖 18
圖2 – 9結晶性高分子材料在不同結晶溫度下Xt 對時間之關係圖 22
圖2-10混合過程中分佈作用之示意圖 27
圖2-11摻合物加工後物性與組成之關係 28
圖圖2-12 DSC thermograms during the second heating scan at 10 ℃/min of PLA-OLA films after processing 29
圖2-13 Structures and compositions of PLA-b-PEG block copolymerssynthesized and used as plasticizers for PLA 32
圖2-14 DSC diagrams of neat PLA and PLA:(COPO4/TBC) compositions with different percentages of plasticizer (%, by weight) 32
圖2-15 MDI結構式 38
圖2-16 PLA/Starch (a)未添加MDI ,(b)添加MDI 混摻之SEM圖 39
圖4-1 (a)PLA, (b) C5,的紅外光譜圖 44
圖4-2 (a) PLAA, (b) C0.5, (c) C1, (d) C3,(e) C5,的紅外光譜圖 44
圖4-3 (a)C5, (b)C3, (c)C1, (d)C0.5, (e)PLAA, (f)PLAAB, (g)PLA 之X-ray性質分析圖 45
圖4-4 (a)PLA, (b)PLAA, (c)PLAAB的DSC熱分析圖 47
圖4-5 (a) C0.25, (b) C0.5 , (c) C1 , (d) C3 , (e) C5 的DSC熱分析圖 52
圖4-6 (a) C0.25, (b)C0.5, (c) C1(d) C3(e)C5在降溫速率0.5℃/min與升溫速率10℃/min的DSC熱分析圖 55
圖4-7 (a) C0.25, (b)C0.5, (c) C1(d) C3(e)C5在降溫速率1℃/min與升溫速率10℃/min的DSC熱分析圖 56
圖4-8 (a) C0.25, (b)C0.5, (c) C1(d) C3(e)C5在降溫速率3℃/min與升溫速 率10℃/min的DSC熱分析圖 57
圖4-9 (a) C0.25, (b)C0.5, (c) C1(d) C3(e)C5在降溫速率5℃/min與升溫速率 10℃/min的DSC熱分析圖 58
圖4-10 (a) C0.25, (b)C0.5, (c) C1(d) C3(e)C5在降溫速率10℃/min與升溫速率10℃/min的DSC熱分析圖 59
圖4-11 Cx 再結晶溫度與成核劑含量關係圖 60
圖4-12 Cx 再結晶熱焓值與成核劑含量關係圖 60
圖4-13 Cx樣品的CRC值比較圖 61
圖4-14 (a)PLA, (b)PLAA, (c)PLAAB的DMA動態機械性質圖 63
圖4-15 PLA和Cx的DMA動態機械性質圖 64
圖4-16 PLA及Cx含量改質聚合物之耐衝擊強度 67
圖4-17 (a)PLA, (b) D10E10,(c)D,(d)E的紅外光譜圖 69
圖4-18 聚乳酸複合膜塑料的紅外光譜圖 70
圖4-19 (a) D20E10, (b) D15E10, (c) D10E10, (d) D5E10, (e) PLA, (f)E, (g)D 之X-ray性質分析圖 72
圖4-20 薄膜基礎塑料(a)D ,(b)PLA, (c)E在升降溫速度10℃/min的二次升降溫熱分析圖 74
圖4-21複合膜(a) D5E10 ,(b) D10E10, (c) D15E10, (d) D20E10的DSC熱分析圖 76
圖4-22 複合膜(a)D10E5 ,(b) D10E10, (c) D10E15的DSC熱分析圖 77
圖4-23 複合膜(a) D10E10 ,(b)D10E10F0.25, (c) D10E10F0.5, (d) D10E10F1.0, (e) D10E10F2.0的DSC熱分析圖 79
圖4-24 複合膜(a) D10E10F2.0 ,(b) D10E10F2.0G10, (c) D10E10F2.0G15的DSC熱分析圖 81
圖4-25 複合膜(a)D15E10 ,(b) D15E10F0.25, (c) D15E10F0.5, (d) D15E10F1, (e) D15E10F 2 的DSC熱分析圖 83
圖4-26 DxE10的DMA動態機械性質圖 85
圖4-27 D10E10、D10E10Fx的DMA動態機械性質圖 87
圖4-28 D10E10F2.00、D10E10F2.00Gx的DMA動態機械性質圖 89
圖4-29薄膜基礎塑料(a)D ,(b)E, (c)PLA的機械性質圖 90
圖4-30 複合膜樣品的應力應變曲線圖 92
圖4-31 PLA，D10E10F2.00G15與D複合膜斷裂延伸率圖 93
圖4-32 PLA複合薄膜 (a)PLA ,(b)D5E10, (c)D10E10,(d) D15E10F0.25, (e)D15E10F1.0, (f)D15E10F2.0的SEM圖 99
圖4-33 UV-vis spectra of PLA and D10E10F2.00 and D10E10F2.0Gx films (film thickness: 30 μm) 100
圖4-33 PLA與D10E10F2.0的Lab座標圖 101






















表目錄
表2-1生物分解性高分子種類及商品 4
表2-2列出目前各國測試生物分解性所用之規範 9
表2-3聚乳酸與其他泛用塑膠材料物性比較 11
表2-4 PLA不同晶型的特性 14
表2-5 PLLA的Hoffman–Lauritzen公式參數 19
表2-6不同成核與成長形態之Avrami 指數 22
表2-7生物分解性材料之應用產品 24
表2-8 Elastic modulus (E), elongation at break (εtB) and oxygen transmission rate per film thickness (OTR*e) of neat PLA and plasticized films after processing. Results are given as average ± standard deviation 30
表2-9 Mechanical properties of neat PLA and PLA plasticized with blends TBC/PLA-b-PEG copolymers 33
表2-10學術上應用於PLA塑化劑之特性 34
表2-11 Average Tg and Tm depression of PLA as a function of plasticizer type and concentration 35
表2-12各種聚合物的力學性能 37
表2-12 PLA/Starch 混摻之DSC熱分析數據 39
表4-1 PLA 、PLAA、PLAAB樣品熱分析數據(10℃/min) 47
表4-2 Cx樣品熱分析數據(10℃/min) 49
表4-3 Cx樣品熱分析數據 55
表4-4 Cx樣品熱分析數據 56
表4-5 Cx樣品熱分析數據 57
表4-6 Cx樣品熱分析數據 58
表4-7 Cx樣品熱分析數據 59
表4-8 PLA、PLAA、PLAAB、Cx之儲存模數 65
表4-9 PLA、PLAA、PLAAB、Cx樣品拉伸強力數據 66
表4-10 PLA、PLAA、PLAAB、Cx樣品耐衝擊分析數據 67
表4-11為DxE10樣品熱分析數據(二次升溫圖) 76
表4-12為D10Ex樣品熱分析數據(二次升溫圖) 78
表4-13 複合膜D10E10與D10E10Fx樣品熱分析數據 79
表4-14 複合膜D10E10F2.0與D10E10F2.0Gx樣品熱分析數據 81
表4-15 複合膜D15E10與D15E10Fx樣品熱分析數據 84
表4-16 薄膜基礎塑料(a)D ,(b)E, (c)PLA的機械性質數據 90
表4-17 複合膜樣品的機械性質數據 91
表4-18 DxE10、D10E10Fx、D15E10Fx與D10E10F2.00Gx耐衝擊試驗試片斷面照片 95
表4-19 複合膜樣品的機械性質數據 97
表4-20 Optical transparency of PLA and D10E10F2.0、D10E10F2.0Gx films 101

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