本研究以熔融插層法藉由混煉機製備聚乳酸/蒙脫土奈米複合材料。以聚氧乙烯山梨糖脂肪酸酯-80 (T80)與二異氰酸異佛爾酮 (IPDI)反應合成插層劑(T80-NH3+)。之後直接將聚乳酸(PLA)、T80-NH3+以及未改質蒙脫土(PK802)用混煉機製備PLA-T80-NH3+-PK802複合材料並與利用改質蒙脫土(Cloisite30B)摻混聚乳酸之複合材料作比較。製備出的複合材料將進行拉力，XRD、TEM、TGA以及DMA的測試，結果發現當PLA加入1 phr Cloisite 30B的含量時，會有塑化的效果，使伸長率上升至208%；以Halpin-Tasi及Mori-Tanaka理論計算得到PLA在加入Cloisite 30B後所得到的蒙脫土片層數為8~15，而此結果是正好符合TEM圖的8~9片；而當PLA直接加入T80-NH3+及PK802各3 phr 的含量時，層間距由純黏土之1.24nm上升至4.93nm，但在加入T80-NH3+及PK802後，高溫會使得T80-NH3+結構上的正電荷與PLA反應而導致裂解；且PK802層間距中所吸附的水層在高溫下也會導致PLA的水解。

In this research, an inorgainic-organic nanocomposite material (PLA /montmorillonite) was prepared by melt intercalation method using a mixer. A kind of modifier called T80-NH3+ was synthesized with Tween80 and IPDI. PLA-T80-NH3+PK802 composites were prepared by pouring PLA、T80-NH3+ and Na+-MMT into a mixer in sequence. Besides, the product will be compared with PLA-C30B-(1 or 3 or 5 or 7phr). By means of some tests, take XRD，TEM、TGA and DMA for example, it was found that the addition of 1 phr Cloisite 30B caused the so-called ‘‘ plasticization effect ’’ which promote the elongation at break to 208%； We could get the numbers of montmorillonite platelet of PLA-Cloisite 30B composites which was calculated by Halpin-Tasi and Mori-Tanaka equations is between eight and fifteen, the result just match the TEM scheme which the numbers of montmorillonite platelet is between eight and nine. The composite of the PLA-T80-NH3+-3-PK802-3 has good ratio of T80-NH3+ to PK802 which result in expansion of the inter-lamellar space from 1.24nm to 4.93nm. A drawback which the structure of T80-NH3+ with the positive charge and the inter-lamellar space of PK802 with water layers lead to the thermal decomposition of PLA appears when the material was prepared.

總目錄
中文摘要	I
英文摘要		III
總目錄	V
圖目錄	VII
表目錄		XI
第一章 序論	1
第二章 基礎理論	3
    2.1生物可分解聚酯類高分子	3
    2.2 蒙脫土的結構性質與分析	4
    2.3 高分子複合材料	7
        2.3.1 傳統複合材料	7
        2.3.2 插層型複合材料	7
        2.3.3 剝離型複合材料	7
        2.3.4 部分插層及部分剝離型複合材料	8
    2.4 以理論公式預測蒙脫土分散於高分子中的行為模式( Modeling )	13
    2.5 X光繞射法原理	21
第三章 實驗材料與方法	25
     3.1 實驗藥品	25
    3.2 實驗儀器	27
    3.3 實驗步驟	29
        3.3.1 反應前處理及配置	29
        3.3.2 插層劑T80-NH3+之合成	30
        3.3.3 蒙脫土之插層過程	32
        3.3.4 製備高分子奈米複合材料	33
    3.4 材料測試與分析	35
        3.4.1 熱壓機製膜	35
        3.4.2 拉力性質測試	35
        3.4.3 熱重損失測試(TGA)	36
        3.4.4 動態機械分析儀測試(DMA)	36
        3.4.5 傅利葉轉換紅外線光譜儀(FTIR)	37
        3.4.6 X光繞射分析儀(XRD)	37
        3.4.7 場發射高解析穿透式電子顯微鏡 (HRTEM)	39
第四章 結果與討論	40
    4.1傅利葉轉換紅外線光譜測試	40
    4.2 Tween80與IPDI的反應機制	52
    4.3 以X光繞射分析儀(XRD)及場發射高解析穿透式電子顯微鏡	63
    4.4 拉力性質測試 (Tensile Test)	77
    4.5 拉力性質理論計算	84
    4.6 熱重損失測試(TGA)	87
    4.7 動態機械分析儀測試(DMA)	94
    4.8 動態機械分析儀理論計算	100
    4.9 結論	110
第五章 參考文獻	112
建議事項	117
附錄	118
    附錄1.1 示差微分掃瞄卡計量測(DSC)	118
    附錄1.2熱重損失測試(TGA)	125
    附錄1.3 結構鑑定及拉力性質測試	130
    附錄1.4 聚乳酸接枝馬來酸酐(PLA-MA)的製備與檢定	137









 
圖目錄
圖2.1高分子量聚乳酸合成示意圖	3
圖2.2蒙脫土結構示意圖	4
圖2.3 HEMA與IPDI的反應示意圖	6
圖2.4 H-HTPI與I-IPDI的化學結構示意圖	7
圖2.5高分子複合材料示意圖: (a)傳統相容, (b)部分插層及剝離, (c)完全插層及
分散, (d)完全剝離及分散	8
圖2.6根據(a) Halpin-Tasi 和(b) Mori-Tanaka 兩個方程式來計算高分子複合材
料在加入不同幾何形狀的蒙脫土後，剛硬性的變化	18
圖2.7不同長徑比(Aspect ratio)的Disk-like Platelet幾何形狀	19
圖2.8高分子奈米複合材料迂迴路徑形成的示意圖	20
圖2.9晶粒繞射的示意圖	22
圖2.10晶粒繞射的曲線圖	23
圖3.1 不同時間下Tween80所測之水損失重	26
圖3.2 以Tween80與IPDI反應合成T80-NH3+的過程示意圖	31
圖3.3不同時間下T80-NH3+所測之水損失重	31
圖3.4製備高分子奈米複合材料之流程圖	34
圖3.5熱壓製膜之示意圖	35
圖3.6製備啞鈴狀拉力試片之示意圖	36
圖4.1 Tween80和IPDI反應前後之紅外線光譜圖，反應溫度為50oC，催化劑(T12)濃度為0.1wt%	41
圖4.2 Tween80和IPDI反應前後之紅外線光譜圖，反應溫度為50oC，催化劑(T12)濃度為0.05wt%	42
圖4.3 Tween80和IPDI反應前後之紅外線光譜圖，反應溫度為50oC，催化劑(T12)濃度為0.1wt%	43
圖4.4 Tween80和IPDI反應前後之紅外線光譜圖，反應溫度為50oC，催化劑(T12)濃度為1wt%	44
圖4.5 Tween80和IPDI反應前後之紅外線光譜圖，反應溫度為50oC，未加入催化劑	45
圖4.6 Tween80和IPDI反應前後之紅外線光譜圖，反應溫度為30oC，催化劑(T12)濃度為0.1wt%	46
圖4.7以GRAMS/AI軟體對波峰作面積積分	50
圖4.8在不同催化劑濃度下的異氰酸酯基團轉化率曲線圖	51
圖4.9在不同反應溫度下的異氰酸酯基團轉化率曲線圖	51
圖4.10 T12(0.1wt%)-30oC的二級反應速率定律式圖	55
圖4.11 T12(0.1wt%)-50oC的二級反應速率定律式圖	56
圖4.12 T12(0.05wt%)-50oC的二級反應速率定律式圖	56
圖4.13 T12(1wt%)-50oC的二級反應速率定律式圖	57
圖4.14 T12(None)-50oC的二級反應速率定律式圖	57
圖4.15 在不同溫度及不同催化劑濃度下的二級反應速率定律式圖	58
圖4.16 以lnk對1/T作圖，求得活化能(Ea)	59
圖4.17 NCO基團轉化率的理論及實驗曲線圖-T12(0.05wt%)-50oC 	60
圖4.18 NCO基團轉化率的理論及實驗曲線圖-T12(0.1wt%)-50oC	60
圖4.19 NCO基團轉化率的理論及實驗曲線圖-T12(1wt%)-50oC	61
圖4.20 NCO基團轉化率的理論及實驗曲線圖-T12(0.1wt%)-30oC	61
圖4.21 NCO基團轉化率的理論及實驗曲線圖-T12(None)-50oC	62
圖4.22 NCO基團轉化率的理論及實驗曲線圖-T12(0.1wt%)-30oC and T12(0.1wt%)-50oC	62
圖4.23 以Tween80分子結構推算層間距	67
圖4.24 未改質蒙脫土(PK802)及改質蒙脫土(Cloisite30B, T80-NH3+-PK802)之
XRD圖	67
圖4.25 PLA-C30B-(1 or 3 or 5 or 7phr)之XRD圖	68
圖4.26 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)之XRD圖	68
圖4.27 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr)之
XRD圖	69
圖4.28 比較PLA-T80-NH3+-5-PK802-5與PLA-T80-OH-5-PK802-5之
XRD圖	69
圖4.29 PLA-T80-NH3+-PK802-(1 or 3 or 5 or 9phr)之XRD圖	70
圖4.30 改質蒙脫土1CEC-T80-NH3+- PK802之TEM圖[(a)~ (c)]	72
圖4.31 改質蒙脫土Cloisite 30B之TEM圖[(a)~ (b)]	73
圖4.32 PLA-C30B-5在不同倍率下之TEM圖[(a)~(f)]	76
圖4.33 PLA-C30B-(1 or 3 or 5 phr)的楊氏係數圖	79
圖4.34 PLA-C30B-(1 or 3 or 5 phr)的伸長率圖	79
圖4.35 PLA-C30B-(1 or 3 or 5 phr)的斷裂強度圖	80
圖4.36 PLA-C30B-(1 or 3 or 5 phr)的降伏強度圖	80
圖4.37 PLA-C30B-(1 or 3 or 5 phr)拉力測試後的樣品	81
圖4.38 PLA-10min.的拉力測試圖	82
圖4.39 PLA-C30B-1的拉力測試圖	82
圖4.40 PLA-C30B-3的拉力測試圖	83
圖4.41 PLA-C30B-5的拉力測試圖	83
圖4.42蒙脫土在經過插層後之示意圖	85
圖4.43以Halpin-Tasi equations推論奈米複合材料中Cloisite 30B的片層數	86
圖4.44以Mori-Tanaka equations推論奈米複合材料中Cloisite 30B的片層數	86
圖4.45 T80-NH3+結構催化了PLA結構的降解(m > n)	88
圖4.46 Na+-MMT結構催化了PLA結構的降解(m > n)	89
圖4.47 PLA-C-30B-(1 or 3 or 5 or 7phr)的TGA圖	89
圖4.48 PLA- C30B-(1 or 3 or 5 or 7phr)的DTG圖	90
圖4.49 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)的TGA圖	91
圖4.50 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)的DTG圖	91
圖4.51 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr)的
TGA圖	92
圖4.52 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr)的
DTG圖	92
圖4.53 PLA-C30B-(1 or 3 or 5 phr)的Tan delta圖 95
圖4.54 PLA-C30B-(1 or 3 or 5 phr)的儲存模數圖 96
圖4.55 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)的Tan delta圖 97
圖4.56 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)的儲存模數圖 97
圖4.57 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr)的
Tan delta圖 98
圖4.58 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr)的儲存模數
圖 98
圖4.59 [(a)~(c)] 當aspect ratio = 2時，以Halpin-Tasi equations推論PLA-C30B-(1
or 3 or 5 phr)的實驗結果 103
圖4.60 [(a)~(c)] 當aspect ratio = 3時，以Halpin-Tasi equations推論PLA-C30B-(1
or 3 or 5 phr)的實驗結果 105
圖4.61 [(a)~(c)] 當aspect ratio = 4時，以Halpin-Tasi equations推論PLA-C30B-(1
or 3 or 5 phr)的實驗結果 107
圖4.62 [(a)~(c)] 當aspect ratio = 5時，以Halpin-Tasi equations推論PLA-C30B-(1
or 3 or 5 phr)的實驗結果 109
附錄圖1 PLA-C30B-(1 or 3 or 5 or 7phr)複合材料第一次升溫程序的DSC圖 118
附錄圖2 PLA-C30B-(1 or 3 or 5 or 7phr)複合材料第二次升溫程序的DSC圖 119
附錄圖3 PLA-C30B-(1 or 3 or 5 or 7phr)複合材料第一次冷結晶程序的DSC圖 119
附錄圖4 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)複合材料第一次升溫程序的
DSC圖 120
附錄圖5 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)複合材料第二次升溫程序的
DSC圖 121
附錄圖6 PLA-T80-NH3+-(1 or 3 or 5 or 7phr) 複合材料第一次冷結晶程序的
DSC圖 121
附錄圖7 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr) 複合材料
第一次升溫程序的DSC圖 122
附錄圖8 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr) 複合材料
第二次升溫程序的DSC圖 123
ATRX-Q03-001-FM031-01
X
附錄圖9 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)-PK802-(1 or 3 or 5 or 7phr) 複合材料
第一次冷結晶程序的DSC圖 123
附錄圖10 插層蒙脫土(T80-NH3+-PK802)經由水洗1次或3次後的TGA圖 125
附錄圖11 插層蒙脫土(T80-NH3+-PK802)經由水洗1次或3次後的DTG圖 126
附錄圖12 Tween80的TGA圖 127
附錄圖13 Tween80的DTG圖 128
附錄圖14未改質蒙脫土(PK802)的TGA圖 128
附錄圖15未改質蒙脫土(PK802)的DTG圖 129
附錄圖16 Biomax之FTIR測試 131
附錄圖17 Biomax之1H譜測試 132
附錄圖18 Biomax之13C譜測試 132
附錄圖19聚乳酸加入不同含量Biomax之楊氏係數 133
附錄圖20聚乳酸加入不同含量Biomax及Cloisite 30B之楊氏係數 133
附錄圖21聚乳酸加入不同含量Biomax之斷裂伸長率 134
附錄圖22聚乳酸加入不同含量Biomax及Cloisite 30B之斷裂伸長率 134
附錄圖23聚乳酸加入不同含量Biomax之降伏強度 135
附錄圖24聚乳酸加入不同含量Biomax及Cloisite 30B之降伏強度 135
附錄圖25聚乳酸加入不同含量Biomax之斷裂強度 136
附錄圖26聚乳酸加入不同含量Biomax及Cloisite 30B之斷裂強度 136
附錄圖27聚乳酸(2002D)接枝馬來酸酐之1H譜圖 143
附錄圖28聚乳酸(sigma aldrich)接枝馬來酸酐之1H譜圖 143

表目錄
表2.1 在某些論點假設下，理論公式計算與實際情形的差異之處 19
表3.1 XRD儀器在不同模式下掃描時，繞射角變化的情形 38
表4.1 Tween80接枝IPDI之特性吸收峰 46
表4.2 不同反應溫度及不同催化劑濃度下的速率常數(k1,k2)值 58
表4.3 不同反應溫度及不同催化劑濃度下的速率常數(k)值及活化能 59
表4.4 PLA-C30B-(1, 3, 5, 7phr)的Td值 90
表4.5 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)及PLA-T80-NH3+-(1 or 3 or 5 or
7phr)-PK802(1 or 3 or 5 or 7phr)之Td值 93
表4.6 PLA-C30B-(1 or 3 or 5 phr)的DMA數值 96
表4.7 PLA-T80-NH3+-(1 or 3 or 5 or 7phr)及PLA-T80-NH3+-(1 or 3 or 5 or
7phr)-PK802-(1 or 3 or 5 or 7phr)的DMA數值 99
附錄表1 不同複合材料第一次升溫程序時的DSC數值 124
附錄表2 不同複合材料第二次升溫程序時的DSC數值 124
附錄表3 改質蒙脫土在T80-NH3+插層後的層間距大小及成分的含量 126
附錄表4 聚乳酸以熔融法接枝馬來酸酐之接枝率 140
附錄表5 聚乳酸以溶液法接枝馬來酸酐之接枝率 141

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