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標題: 聚對苯二甲酸丁二酸丁二酯共聚合物/有機改質層狀苯基磷酸鋅奈米複合材料之製備與特性分析
Preparation and characterization of organically modified layered zinc phenylphosphonate/ poly(butylene succinate-co-terephthalate) nanocomposites
作者: 林聖翔
Sheng-Hsiang Lin
關鍵字: 聚對苯二甲酸丁二酸丁二酯共聚合物;層狀苯基磷酸鋅;奈米複合材料;等溫結晶行為;微結構;生物降解性;Poly(butylene succinate-co-terephthalate);Layered zinc phenylphosphonate;Nanocomposites;Crystalline behaviors;Microstructure;Biodegradable
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聚對苯二甲酸丁二酸丁二酯共聚合物(Poly(butylene succinate-co-terephthalate),PBST)為對苯二甲酸和琥珀酸組合之共聚物,屬於半結晶且微生物可分解之材料,可被微生物分解成水和二氧化碳,此外,本研究添加具補強效果之無機材料層狀苯基磷酸鋅製備出生物可分解奈米複合材料以增加其應用方面與使用價值。
首先利用共沉澱法製備層狀苯基磷酸鋅(Layered Zinc Phenylphosphonate,PPZn),並使用化學改質法將己烷二胺及十二烷基二胺插層進入PPZn形成有機改質C6-PPZn和C12-PPZn。利用XRD研究 PPZn與其改質PPZn在(0 1 0)繞射平面之繞射峰位置,PPZn未插層之層間距為14.34 Å,改質後C6-PPZn和C12-PPZn分別增加至22.31和16.07 nm,由FT-IR圖譜得知改質PPZn較未改質PPZn多了額外吸收峰在波數為2853-3005和1650-1550是因為長鏈烷基胺所致,經由上述之數據證明本實驗成功使用化學改質法形成較大層間距之層狀PPZn。
經由溶劑插層法將PBST-g-AA與不同比例之C12-PPZn、C16-PPZn和C18-PPZn形成奈米複合材料,由XRD圖譜及TEM影像可以判斷改質PPZn以部分剝離與部分插層且隨機分散於PBST 基材中,形成奈米複合材料且添加改質PPZn並部會改變PBST之結晶結構。
降解測試為利用假單胞菌(Lipase from Pseudomonas fluorescens)酵素酶作為降解液,再進行PBST及其奈米複合材料之生物降解測試,觀察其重量損失與降解時間之變化,得知PBST之降解速率會隨著改質PPZn含量上升而降解速率越快,而以改質PPZn相比,C6-PPZn之降解速率較快,主要原因是為PBST/C6-PPZn結晶度較低,造成其降解速率較快。

Poly(butylene succinate-co-terephthalate) (PBST), a semicrystalline copolymer and biodegradable, can be synthesized using terephthalic acid and butylene succinic acid. Biodegradable PBST can be degraded by microorganisms to form carbon dioxide and water. For the purpose of enhancing the physical properties of PBST, the inorganic layered zinc phenylphosphonate (PPZn) was added into the PBST polymer matrix.
In this work, the organically-modified layered zinc phenylphosphonate prepared using coprecipitation method were sucessfully synthesized to intercalate diaminohexane and dodecanediamine into the interlayer spacing of PPZn (designated as C6-PPZn and C12-PPZn). The interlayer spacing of PPZn determined by wide-angle X-ray diffraction (WAXD) was increased from 14.34 Å for PPZn to 22.31 and 16.07 Å for C6-PPZn and C12-PPZn, respectively. The FT-IR spectra of modified-PPZn contain absorption bands at 2830-3000 and 1650-1550 cm-1 for the C-H stretching vibration and NH2 deformation of diaminohexane and dodecanediamine. Compare to that PPZn, the additional absorption peaks are attributed to diaminohexane and dodecanediamine in corporation into PPZn.
The PBST-g-AA/modified-PPZn nanocomposites were prepared by solvent intercalation method. The structure and morphology of the PBST-g-AA/modified-PPZn nanocomposites were characterized using WAXD and transmission electron microscopy (TEM). Both WAXD and TEM results demonstrate that most of the partial-delamination modified-PPZn was randomly dispersed in the PBST matrix and the incorporation of modified-PPZn into PBST did not change the crystalline structure of the nanocomposites.
Crystallization behavior was performed using the differential scanning calorimetry (DSC). The n value of nanocomposite is close to 2, suggesting that the PBST spherulite grows with a 2-dimensional structure.
Degradation tests using Lipase from Pseudomonas fluorescens as the enzyme enzymatic degradation solution. The weight loss of PBST increase with an increase in the content of modified-PPZn. The C6-PPZn nanocomposites has a faster degradation rate. This result is probably due to the lower degree of crystallinity for C6-PPZn nanocomposites.
The PBST and its nanocomposites with porous morphology were successfully fabricated by combining pseudo steady state unidirectional freezing and freeze-drying techniques. The weight loss of PBST increase with an increase in the content of modified-PPZn.
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