臺灣博碩士論文加值系統

聚己二酸二丁酯(Poly(Butylene adipate)，PBA)作為脂肪族聚酯，也是一種可生物分解高分子，並具有多晶型晶體結構，然而添加25mol%以下之BT單元時可形成屬於PBA相聚丁烯己二酸對苯二甲酸酯(Poly(Butylene adipate-co-terethphalate)，PBAT)共聚酯。本研究透過兩階段製備合成出三種比例之PBAT，分別為PBA、PBAT90及PBAT80，並以丙烯酸接枝於高分子鏈上增加無機物與高分子基材間相容性，且利用共沉澱法製備不同碳鏈烷基二酸改質層狀雙氫氧化物C6-LDH與C12-LDH，由XRD分析結果其層間距由8.3 Å增加至13 Å及16.3 Å，另外由FTIR圖譜觀察到改質後之LDH顯示新的特徵峰在波數為2925 cm-1、2854 cm-1及1558 cm-1處，同時原本屬於層間陰離子硝酸根訊號減弱，表示改質劑烷基二酸成功插層進入LDH層間。再經由溶劑插層法製備1、3及5wt%之g-PBAT/C6-LDH與C12-LDH奈米複合材料，透過XRD與TEM顯示出改質LDH以剝離型態分散於PBAT基材中，且添加LDH與接枝不會改變PBAT之結構。由TGA分析PBAT及其奈米複合材料之熱穩定性，觀察到由於LDH板層中鎂鋁金屬會催化裂解，導致奈米複合材料熱裂解溫度往低溫位移，說明其熱穩定性下降。由DMA探討LDH對其機械性質之影響，結果顯示C6-LDH與C12-LDH隨著添加比例增加呈現上升趨勢，由於剛硬LDH板層增強效果提升PBAT之剛性。透過DSC觀察添加不同比例C6-LDH及C12-LDH對於PBAT之等溫結晶行為影響，發現添加改質LDH使PBAT半結晶時間縮短。利用DSC、XRD及POM觀察不同結晶溫度下之晶體結構，由於BT單元加入使PBAT多晶型晶相轉變溫度往低溫位移，再探討LDH添加對於PBAT晶相轉變影響，由結果顯示添加C6-LDH及C12-LDH對PBAT晶相轉變溫度區間無明顯變化。

Poly(butylene adipate) (PBA), an aliphatic polyester and biodegradable polymer, shows a polycrystalline crystal structure. In order to enhance the physical properties of PBA, the addition of rigid unit such as butylene terephthalate (BT) can reach this approach. However, when the addition of BT unit is below 25 mol%, poly(butylene adipate-co-terephthalate) (PBAT) copolyester belonging to the PBA crystalline phase can be formed. In this study, PBAT has been synthesized from 1,4 butanediol, adipic acid and dimethyl terephthalate via a two-step synthesis procedure using titanium butoxide as a catalyst. Then, the acrylic acid was grafted onto PBAT polymer chain (g-PBAT) and the organically modified LDH was successfully synthesized to intercalate two different alkyl diacid into the interlayer space using co-precipitation method (designated as C6-LDH and C12-LDH) to improve the compatibility and dispersibility between the polymer matrix and LDH. According to the XRD results, the interlayer spacings of LDH increased from 0.84 nm for the LDH to 1.3 nm and 1.63 nm for the C6-LDH and C12-LDH, respectively. The FT-IR spectra show that m-LDHs contained both functional groups of organical modifier and LDH. These data confirm that the modifier of dialkyl acid has successfully intercalated into the LDH layer by co-precipitation method. The g-PBAT/m-LDH nanocomposites were prepared by solvent intercalation. The structure and morphology of PBAT/m-LDH nanocomposites were characterized by XRD and TEM. The results of WAXD and TEM showed that the modified LDH was dispersed in PBAT matrix. The addition of organically modified LDH into PBAT would not change the crystalline structure of the nanocomposites. TGA analysis also showed that both m-LDH caused a decrease in thermal stability of PBAT due to the catalytic effect of Mg and Al metals of LDH. The mechanical properties were discussed by DMA analysis. The results show that the incorporation of C6-LDH and C12-LDH increase the rigidity of PBAT with increasing the loading of the rigid LDH layers. The results of isothermal crystallization show that the crystallization rate increases when the incorporation of m-LDH in nanocomposites increases. Use DSC, XRD and POM to observe the crystal structure at different crystallization temperatures. Due to the addition of BT unit, the polymorphic phase transition temperature of PBAT shifts to low temperature. To explore the effect of additional m-LDH on the transformation of PBAT crystal phase, the experimental results of DSC, XRD and POM show that the addition of m-LDH has no significant change in the PBAT crystal phase transition temperature range.

摘要 i
Abstract ii
目錄 iv
表目錄 viii
圖目錄 x
第一章 緒論與簡介 1
1.1 前言 1
1.2 生物可分解高分子簡介 2
1.3 聚己二酸二丁酯 ( Poly ( Butylene adipate)，PBA )簡介 4
1.4 聚丁烯己二酸對苯二甲酸共聚酯( Poly ( Butylene adipate-co-terephthalate )，PBAT )簡介 8
1.5 層狀雙氫氧化物 ( Layer double hydroxide，LDH ) 10
1.6 研究動機與方向 13
第二章 文獻回顧 14
2.1 有機/無機奈米複合材料簡介 14
2.2 高分子PBA/PBAT奈米複合材料 16
2.3 層狀雙氫氧化物(LDH)與高分子奈米複合材料介紹 24
2.3.1 層狀雙氫氧化物(Layered double hydroxides，LDH)之改質 24
2.4 高分子接枝之複合材料 29
2.4.1 層狀雙氫氧化物(LDH)/高分子奈米複合材料 33
2.5 高分子結晶動力學 38
2.5.1 Avrami方程式 40
第三章 實驗方法與步驟 42
3.1 實驗材料 42
3.2 實驗儀器 44
3.3 實驗架構 45
3.4 實驗步驟 46
3.4.1 聚丁烯己二酸對苯二甲酸酯之製備 46
3.4.2 聚丁烯己二酸對苯二甲酸酯共聚物接枝之製備 47
3.4.3 聚丁烯己二酸對苯二甲酸酯共聚物接枝丙烯酸之接枝率測量 47
3.4.4 鎂鋁層狀雙氫氧化物之製備 48
3.4.5 有機改質鎂鋁層狀雙氫氧化物之製備 48
3.4.6 聚丁烯己二酸對苯二甲酸酯/有機改質鎂鋁層狀雙氫氧化物奈米複合材料之製備 49
3.5 實驗分析儀器 50
3.5.1 傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer，FTIR) 50
3.5.2 超導磁場核磁共振儀（ Nuclear Magenetic Resonance，NMR） 50
3.5.3 膠體滲透層析儀(Gel Permeation Chromatography，GPC) 50
3.5.4 廣角X光繞射儀(Wide Angle X-Ray Diffraction，WAXD) 51
3.5.5 式差掃描式熱分析儀 (Different scanning calorimeter，DSC) 51
3.5.6 熱重分析儀（Thermogravimetric analysis，TGA） 51
3.5.7 偏光顯微鏡(Polarizing Optical Microscope，POM) 52
3.5.8 穿透式電子顯微鏡 (Transmission Electron Microscope，TEM) 52
3.5.9 動態力學分析儀(Dynamic Mechanical Analsis，DMA) 52
第四章 結果與討論 53
4.1 MgAl-LDH製備與改質分析 53
4.2 MgAl-LDH及其有機改質LDH之熱性質分析 56
4.3 聚己二酸二丁酯PBA及其奈米複合材料之性質研究與探討 59
4.3.1 聚己二酸二丁酯PBA之組成與結構鑑定 59
4.3.2 聚己二酸二丁酯接枝g-PBA之鑑定分析 61
4.3.3 g-PBA添加C6-LDH及C12-LDH奈米複合材料之分散性探討 65
4.3.4 g-PBA添加C6-LDH及C12-LDH奈米複合材料之熱性質探討 68
4.3.5 g-PBA添加C6-LDH及C12-LDH奈米複合材料機械性質探討 71
4.3.6 g-PBA添加C6-LDH奈米複合材料之等溫結晶行為探討 74
4.3.7 g-PBA添加C12-LDH奈米複合材料之等溫結晶行為探討 78
4.3.8 g-PBA添加C6-LDH及C12-LDH奈米複合材料之不同溫度區間結晶型態 82
4.4 聚丁烯己二酸對苯二甲酸酯PBAT90其奈米複合材料之性質研究與探討 94
4.4.1 聚丁烯己二酸對苯二甲酸酯PBAT90之組成與結構鑑定 94
4.4.2 聚丁烯己二酸對苯二甲酸酯接枝g-PBAT90之鑑定分析 96
4.4.3 g-PBAT90添加LDH之奈米複合材料之分散性探討 99
4.4.4 g-PBAT90添加C6-LDH及C12-LDH之奈米複合材料之熱性質分析 102
4.4.5 g-PBAT90添加C6-LDH及C12-LDH奈米複合材料之機械性質探討 105
4.4.6 g-PBAT90添加C6-LDH奈米複合材料之等溫結晶行為探討 108
4.4.7 g-PBAT90添加C12-LDH奈米複合材料之等溫結晶行為探討 112
4.4.8 g-PBAT90添加LDH之奈米複合材料不同溫度區間結晶型態 116
4.5 聚丁烯己二酸對苯二甲酸酯PBAT80及其奈米複合材料之性質研究與探討 127
4.5.1 聚丁烯己二酸對苯二甲酸酯PBAT80之組成與結構鑑定 127
4.5.2 聚丁烯己二酸對苯二甲酸酯接枝g-PBAT80之鑑定分析 129
4.5.3 g-PBAT80添加LDH之奈米複合材料之分散性探討 133
4.5.4 g-PBAT80添加C6-LDH及C12-LDH之奈米複合材料之熱性質分析 136
4.5.5 g-PBAT80添加C6-LDH及C12-LDH奈米複合材料之機械性質探討 139
4.5.6 g-PBAT80添加C6-LDH之奈米複合材料之等溫結晶行為 142
4.5.7 g-PBAT80添加C12-LDH之奈米複合材料之等溫結晶行為 146
4.5.8 g-PBAT80添加LDH之奈米複合材料不同溫度區間結晶型態 150
第五章 結論 161
參考文獻 163

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