成核劑表面改質對聚-3-羥基丁酸酯之結晶與劣化性質影響研究

Effects of the surface treatments of inorganic fillers on the crystallization and thermal degradation properties of polyhydroxybutyrate

黃士哲(Shih-Che Huang)

指導教授 ： 洪信國

元智大學/工程學院/化學工程與材料科學學系/碩士(2009年)

https://doi.org/10.6838/YZU.2009.00294

摘要

本研究為探討聚-3-羥基丁酸酯(Polyhydroxybutyrate, PHB)掺混不同成核劑後的熱性質與結晶性質，利用傅式紅外線光譜儀(Fourier Transform Infrared Spectroscopy, FT-IR)分析成核劑改質前後的官能基變化，由熱重量分析儀(Thermogravimetric Analysis, TGA)分析純化前後PHB及掺混各種成核劑後的熱性質變化，再由示差掃描熱分析儀(Differential Scanning Calorimetry, DSC)研究其動態結晶行為，利用恆溫結晶動力與非恆溫結晶動力對各樣品做進一步結晶探討。偏光顯微鏡(Polarized Optical Microscopy, POM)觀察各樣品之結晶大小形狀，X-ray繞射儀(X-ray Diffraction, XRD)觀察各樣品晶格結構與晶格變化。純化PHB可提升初始劣解溫度與最大劣解溫度，成核劑中以掺混Hydrophobic Silica(R812)-2 PHR後能提升最大裂解溫度及提升最多結晶速率與結晶量，掺混接枝Poly amide(PA)後Hydrophilic Silica(A300)提升次多結晶速率，且使PHB材料生成較完美結晶，POM觀察出PHB樣品結晶為球晶型態，且摻混成核劑後成核密度上升，使PHB平均球晶大小下降。XRD結果顯示掺混各成核劑後晶型結構無明顯變化，掺混A300後晶格大小降低，掺混其他成核劑後晶格大小皆提昇。

關鍵字

聚-3-羥基丁酸酯 ； 結晶 ； 劣化 ； 表面處理 ； 動力

並列摘要

The effects of the surface treatments of inorganic fillers on the crystallization and thermal degradation properties of polyhydroxybutyrate (PHB) are studied using differential scanning calorimetry (DSC), Fourier transformed infrared spectroscopy (FTIR), polarized light microscope (POM), wide angle x-ray diffraction (WAXD), and themgravimetric analysis (TGA). From FTIR and TGA analyses, it is indicated that the fumed silica can be effectively grafted with the reactive silanes and long chain amides. The thermal degradation of PHB can be significantly improved by the addition of only one part per hundred PHB (phr) inorganic silica or other modified silica. The results of DSC indicate that PHB with 2 phr hydrophobic silica can have the greatest increases of the thermal stability, crystallization rate, and crystallinity. The use of the amide modified silica can effectively decrease the melt-recrystallization extent of PHB near the melting temperature. The crystal size of PHB decreases with the addition of the silica. The crystallization kinetic parameters of PHB are also changed by the type of silica added.

並列關鍵字

polyhydroxybutyrate ； crystallization ； degradation ； surface treatment ； DSC ； kinetics

參考文獻

3. Z. Gan, H. Abe, Y. Doi, “Crystallization, Melting, and Enzymatic Degradation of Biodegradable Poly(butylene succinate-co-14 mol ethylene succinate) Copolyester”, Biomacromolecules, 2, 313-321 (2001)

7. N. Grassie, E. J. Marray, P. A. Holmes, “The Thermal Degradation of Poly(-(D)-β-hydroxybutyric acid): Part2—Changes in Molecular Weight”, Polymer Degradation and Stability, 6, 95-103 (1984)

8. N. Grassie, E. J. Marray, P. A. Holmes, “The Thermal Degradation of Poly(-(D)-β-Hydroxybutyric Acid): Part 1 Identification and Quantitative Analysis of Products”, Polymer Degradation and Stability, 6, 47-61 (1984)

9. N. Grassie, E. J. Marray, P. A. Holmes, “The Thermal Degradation of Poly(-(D)-β-Hydroxybutyric Acid): Part 3 The Reaction Mechanism”, Polymer Degradation and Stability, 6, 127-134 (1984)

11. L. H. Palys, P. J. Phillips. , “Microkinetics of Crystallization in Poly(ethylene terephthalate)”, Journal of Polymer Science: Part B: Polymer Physics, 18, 829-852 (1980)