臺灣博碩士論文加值系統

本研究以水解小分子聚-3-羥基丁酸酯(Polyhydroxybutyrate, PHB) 與矽酸乙酯(Tetraethyl orthosilicate, TEOS) 以溶膠─凝膠法(Sol-gel) 製備奈米矽複合材，再將此奈米矽複合材與聚乳酸 (Polylactic acid, PLA) 以澆鑄法(Casting) 混合，並探討其性質與應用，由傅式紅外線光譜儀(FT-IR) 分析得知小分子量的聚-3-羥基丁酸酯為水解而非熱裂解產物且與矽酸乙酯成功接枝；凝膠滲透層析儀(GPC) 與核磁共振儀(H1NMR) 得知其數目平均分子量(Mn) 及重量平均分子量(Mw) 分別為1482(g/mol)、2224(g/mol)；熱重量分析儀(TGA) 得知與TEOS反應後接枝重量比大約為25 wt% 及膜材熱穩定性隨著添加劑比例上升而降低；示差掃描熱分析儀(DSC) 得知接枝後結晶速率較快，結晶也較完整。

The preparation of organic-nano silica compound formed by reacting low molecular weight poly-3-hydroxybutyrate (LMWPHB) prepared by the high temperature hydrolysis method with tetraethyl orthosilicate (TEOS) through sol-gel process, and subsequently used the compound as a nucleating agent in polylactic acid (PLA) were studied by using Fourier transformed infrared spectroscopy, Differential Scanning Calorimetry, thermogravimetric analysis, proton NMR, mechanical test, biodegradation test, and gel permeation chromatography. The LMWPHB prepared had Mn and Mw near 1482 and 2224 g/mol, respectively. The OH groups in the LMWPHB could react with TEOS to form nano silica grafted LMWPHB containing 25 wt.% silica with the particle size of silica about 50~60 nm. . The addition of nano silica grafted LMWPHB in PLA would decrease the mechanical properties and biodegradation rate but increase the crystallization rate of PLA.

摘要 I
Abstract II
致謝 III
第一章、緒論 1
1.1前言 1
1.2研究動機與方向 3
第二章、文獻回顧 4
2.1可分解性塑膠簡介 4
2.2生物可分解材料分類 6
2.3聚-3-羥基丁酸酯(PHB)簡介 8
2.4 PHB熱性質 11
2.5 PHB塑化劑 13
2.6 高分子結晶 15
2.6.1 高分子材料的再結晶性質 18
2.7 PHB分解機制 20
2.8 製做小分子PHB的方法 22
2.9 奈米複合材料 24
2.10 Silica之應用 25
2.11 聚乳酸(PLA) 簡介 25
2.13 聚乳酸(PLA) 熱性質與結晶性質 26
2.14 聚乳酸(PLA) 生物降解性質 29
第三章、理論分析 31
3.1凝膠滲透層析儀( Gel Permeation Chromatography , GPC ) 31
3.2示差掃描熱分析儀( Differential Scanning Calorimetry, DSC ) 33
3.3熱重量分析儀(Thermogravimetric Analysis, TGA ) 33
3.4傅式紅外線光譜儀( Fourier Transform Infrared Spectroscopy, FT-IR ) 34
3.5核磁共振儀(Nuclear Magnetic Resonance) 35
3.6萬能材料拉力機 (Universal Material Testing Machine) 36
3.7掃描式電子顯微鏡（Scanning Electron Microscope, SEM） 36
3.8X光繞射分析儀(X-ray diffraction, XRD) 37
3.8.1 Scherrer analysis 37
3.9掃描式電子顯微鏡（Scanning Electron Microscope, SEM） 38
第四章、實驗部分 39
4.1 實驗藥品 39
4.2 儀器設備 41
4.3 實驗步驟 43
4.3.1水解小分子聚-3羥基丁酸酯 (LMW PHB) 之製備 43
4.3.2 改質LMW PHB製備 46
4.3.3 聚乳酸 (PLA) 摻混添加劑膜材製作 49
第五章、結果與討論 52
第一部分 52
水解LMW PHB的分析 52
5.1.1 水解小分子PHB (LMW PHB) FT-IR分析 52
5.1.2 水解小分子PHB (LMW PHB) GPC分析 53
5.1.3 水解小分子PHB (LMW PHB) TGA分析 53
5.1.4 水解小分子PHB (LMW PHB) NMR分析 53
第二部分 55
改質水解LMW PHB 分析 55
5.2.1改質水解LMW PHB FT-IR分析 55
5.2.2改質水解LMW PHB TGA分析 55
5.2.3改質水解LMW PHB DSC分析 56
5.2.4改質水解LMW PHB NMR分析 56
第三部分 58
聚乳酸 (PLA) 摻混添加劑膜材分析 58
5.3.1聚乳酸 (PLA) 摻混添加劑膜材TGA分析 58
5.3.2聚乳酸 (PLA) 摻混添加劑膜材DSC分析 58
5.3.3聚乳酸 (PLA)摻混添加劑膜材拉力分析 59
5.3.4聚乳酸 (PLA)摻混添加劑膜材生物降解性探討 59
5.3.5聚乳酸 (PLA)摻混添加劑膜材XRD分析 60
5.3.6聚乳酸 (PLA)摻混添加劑膜材結晶動力式探討 60
5.3.7分散性探討 63
第六章、結論 64
第七章、參考文獻 65

[1] Q. Qin, Y. Liu, S.-C. Chen, F.-Y. Zhai, X.-K. Jing, and Y. Z. Wang, "Electrospinning Fabrication and Characterization of Poly(vinyl alcohol)/Layered Double Hydroxides Composite Fibers," Journal of Applied Polymer Science, vol. 126, pp. 1556-1563, 2012.
[2] A. Campos, J. M. Marconcini, S. M. Martins-Franchetti, and L. H. C. Mattoso, "The influence of UV-C irradiation on the properties of thermoplastic starch and polycaprolactone biocomposite with sisal bleached fibers," Polymer Degradation and Stability, vol. 97, pp. 1948-1955, 2012.
[3] Z. Abbasi, "Water resistance, weight loss and enzymatic degradation of blends starch/polyvinyl alcohol containing SiO2 nanoparticle," Journal of the Taiwan Institute of Chemical Engineers, vol. 43, pp. 264-268, 2012.
[4] F. V. Pereira, M. C. d. Santos, P. P. d. Souza, J. P. B. Roa, and R. L. Orefice, "Increasing the Elongation at Break of Polyhydroxybutyrate Biopolymer: Effect of Cellulose Nanowhiskers on Mechanical and Thermal Properties," Journal of Applied Polymer Science, vol. 127, pp. 3613-3621, 2013.
[5] B. Gupta, R. Agarwal, and M. S. Alam, "Preparation and Characterization of Polyvinyl Alcohol-Polyethylene Oxide-Carboxymethyl Cellulose Blend Membranes," Journal of Applied Polymer Science, vol. 127, pp. 1301-1308, 2013.
[6] 黃振燦, "生物可分解塑膠," 美國飼料穀物協會, pp. 5-9, 1997.
[7] Z. Gan, H. Abe, Y. Doi, " Crystallization, Melting, and Enzymatic Degradation of Biodegradable Poly( butylene succinate-co-14 molethylene succinate) Copolyester" , Biomacromolecules, vol. 2, 313-321, 2001.
[8] 柯志強, "生物可分解塑膠之發展與認識", 美國飼料穀物協會, pp. 1-13, 1998.
[9] 李碧洲, " 分解性塑膠的回顧與展望" , 塑膠資訊, vol. 47, p. 36, 2000.
[10] M. Lemoigne, "Etudes sur autolyse microphone acidification par formation acide β-oxybutyrique" , Ann Inst Pasteur, vol. 39, pp. 144, 1925.
[11] 陳國強, "聚羥基脂肪酸酯生態產業鏈-生產與應用技術指南" 化學工業出版社, pp. 259-278, 2008.
[12] N. Grassie, E. J. Marray, P. A. Holmes, " The Thermal Degradation of Poly(-(D)-β-Hydroxybutyric Acid) : Part 2 Changes in Molecular Weight" , Polym. Degrad. Stab, vol. 6, pp. 95-103, 1984.
[13] 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" , Polym. Degrad. Stab, vol. 6, pp. 47-61, 1984.
[14] N. Grassie, E. J. Marray, P. A. Holmes, " The Thermal Degradation of Poly(-(D)-β-Hydroxybutyric Acid) : Part 3 The Reaction Mechanism" , Polym. Degrad. Stab, vol. 6, pp. 127-134, 1984.
[15] 林家豪, " 改質聚-3-羥基丁酸酯之熱性質探討" , 元智大學碩士論文, 2007.
[16] 陳國強, " 聚羥基脂肪酸酯生態產業鏈" 化學工業出版社, 北京, pp. 243-247, 2008.
[17] L. H. Sperling, " Introduction to Physical Polymer Science" , Wiley, Hoboken NJ, p. 231, 1980.
[18] M. S. Jerold, " Self-induced Field Model for Crystal Twisting in Spherulites" , Polymer, vol. 44, pp. 431-441, 2003.
[19] 邱秀榮, 游建文, " Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) / PMMA摻合物非等溫結晶行為及其晶體熔化之研究(II) " , 大華技術學院化學工程系, 國科會計畫標號: NSC 91- 2216 -E- 233- 001, 2002.
[20] K. D. Clerck, H. Rahier, B. V. Mele, P. Kiekens, " Thermal Properties Relevant to the Processing of PET Fibers" , J. Appl. Polym. Sci, vol. 89, pp. 3840-3849, 2003.
[21] W. K. Lee, T. Iwata, H. Abe, Y. Doi, " Visualization of the Recrystallization of Solution-Grown Poly[(R)-3-hydroxybutyrate] Lamellar Crystals" , Macromol. Rapid. Comm, vol. 22, pp. 629-632, 2001.
[22] L. M. W. K. Gunaratne, R. A. Shanks, G. Amarasingle, " Thermal History Effects on Crystallisation and Melting of Poly(3-hydroxybutyrate) " , Thermochimica Acta, vol.423, pp.127-135, 2004.
[23] T. Iwata, Y. Doi, " Structure and enzymatic degradation of poly(3-hydroxybutyrate) copolymer single crystals with an extracellular PHB depolymerase from Alcaligenes faecalis T1" , Int. J. Biol. Macromol , vol. 25 , pp. 169–176, 1999.
[24] H. Ariffin, H. Nishida, Y. Shirai, M. A. Hassan, " Determination of multiple thermal degradation mechanisms of poly(3-hydroxybutyrate) " , Polymer Degradation and Stability, vol. 93, p. 1433, 2008.
[25] J. Yu, D. Plackett, L. X. L. Chen, " Kinetics and mechanism of the monomeric products from abiotic hydrolysis of poly((R)-3-hydroxtbutyrate) under acidic and alkaline conditions" , vol. 89, pp. 289-299, 2005.
[26] G. Yu. , R. H. Marchessault, " Characterization of low molecular weight poly(b-hydroxybutyrate)s from alkaline and acid hydrolysis" , Polymer, vol. 41, pp. 1087-1098 , 2000.
[27] Z. S’pitalsky, I. Lacı´k, E. Lathova´, I. Janigova´, I. Choda´k, " Controlled degradation of polyhydroxybutyrate via alcoholysis with ethylene glycol or glycerol" , Polym. Degrad. Stab. , vol. 91, p. 856, 2006.
[28] G. E. Yu, United States Patent Application Publication, 11/ 129, 479, 2005.
[29] J. Yu, D. Plackett, L. X. L. Chen, " Kinetics and mechanism of the monomeric products from abiotic hydrolysis of poly[(R)-3-hydroxybutyrate] under acidic and alkaline conditions" , Polym. Degrad. Stab. , vol. 89, p. 289, 2005.
[30] B. Sssd, O. M. Keiser, M. Welti, G. K. Uhlschmid, P. Neuenschwander, U. W. Suter, " Multiblock copolyesters as biomaterials: in vitro biocompatibility testing" , J. Mat. Sci.: Mat. in Medicine, vol. 8, p. 497, 1997.
[31] H. Erduranli, B. Hazer, M. Borcakli, " Post Polymerization of Saturated and Unsaturated Poly(3-hydroxy alkanoate)s" , Macromol. Symp. , vol. 269, p. 161, 2008.
[32] G. R. Saad, H. Seliger, " Biodegradable copolymers based on bacterial Poly((R)-3-hydroxybutyrate) : thermal and mechanical properties and biodegradation behaviour" , Polym. Degrad. Stab. , vol. 83, p. 101, 2004.
[33] D. Seebach, M. G. Fritz, " Detection, synthesis, structure, and function of oligo(3-hydroxyalkanoates) : contributions by synthetic organic chemists" , Inter. J. Bio. Macromol. , vol. 25, p. 217, 1999.
[34] Q. Zhao, G. Cheng, " Preparation of biodegradable poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers" , Journal of Materials Science, vol. 39, p. 3829, 2004.
[35] S. Nguyen, R. H. Marchessault, " Graft copolymers of methyl methacrylate and poly([R]-3-hydroxybutyrate) macromonomers as candidates for inclusion in acrylic bone cement formulations: Compression testing" , J. Biomed. Mater. Res. B Appl. Biomater. , vol. 77, p. 5, 2006.
[36] X. Gao, J. C. Chen, Q. Wu, G. Q. Chen, " Polyhydroxyalkanoates as a source of chemicals, polymers, and biofuels" , Current Opinion in Biotechnology, vol. 22, p. 768, 2011.
[37] B. Hazer, Inter. J. Polym. Sci. , doi: 10. 1155/2010/423460, Article ID 423460, 2010.
[38] G. Li, Y. Liu, D. Li, L. Zhang, K. Xu, " A comparative study on structure-property elucidation of P3/4HB and PEG-based block polyurethanes" , J. Biomed. Mater. Res. A , vol. 100A, p. 2319, 2012.
[39] H. Qiu, D. Li, X. Chen, K. Fan, W. Ou, K. C. Chen, K. J. Xu, " Synthesis, characterizations, and biocompatibility of block poly(ester-urethane)s based on biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P3/4HB) and poly(ε-caprolactone) " , Biomedical Materials Research Part A , vol 101A, p. 75, 2013.
[40] S. Dai, Z. Li, " Enzymatic Preparation of Novel Thermoplastic di-Block Copolyesters Containing Poly[(R)-3-hydroxybutyrate] and Poly(ϵ-Caprolactone) Blocks via Ring-Opening Polymerization " , Biomacromolecules, vol. 9, p. 1883, 2008.
[41] J. Brzeska, P. Dacko, K. Gebarowska, H. Janik, B. Kaczmarczyk, J. Kasperczyk, M. Kowalczuk, M. Maria Rutkowska, " The structure of novel polyurethanes containing synthetic poly[(R,S)-3-hydroxybutyrate] " , Applied Polymer Science , vol. 125, p. 4285, 2012.
[42] 徐國財, " 奈米複合材料" , 五南圖書出版股份有限公司, pp. 5-6, 2004.
[43] S. J. LUE, J.-Y. CHEN, and J. M. YANG, " Crystallinity and Stability of Poly(vinyl alcohol) Fumed Silica Mixed Matrix Membranes" , Macromolecular Science, Part B: Physics, vol. 47, pp. 39-51, 2008.
[44] L. J. Han, C. Y. Han, W. L. Cao, X. M. Wang, J. J. Bian, L. S. Dong, " Preparation and Characterization of Biodegradable Poly(3 -hydroxybutyrate-co-4-hydroxybutyrate)/Silica Nanocomposites" , Polymer engineering and science, pp. 250-258, 2012.
[45] M. D. Sanchez-Garcia, E. Gimenez, J. M. Lagaron, " Morphology and Barrier Properties of Nanobiocomposites of Poly(3-hydroxybutyrate) and Layered Silicates" , Applied Polymer Science, vol. 108, pp. 2787-2801, 2008.
[46] P. M. Ma, R. Y. Wang, S. F. Wang, Y. Zhang, Y. X. Zhang, D. Hristova, " Effects of Fumed Silica on the Crystallization Behavior and Thermal Properties of Poly(hydroxybutyrate-co-hydroxyvalerate)" , Applied Polymer Science, vol. 108,pp. 1770-1777, 2008.
[47] K. A. M. Thakur, R. T. Kean, J. M. Zupfer, N. U. Buehler, M. A. Doscotch, E. J. Munson, " Solid State 13C CP-MAS NMR Studies of the Crystallinity and Morphology of Poly(L-lactide) " , Macromolecules, vol. 29, p. 8844, 1996.
[48] H. Urayama, T. Kanamori, K. Fukushima, Y. Kimura, "Controlled crystal nucleation in the melt-crystallization of poly(L-lactide) and poly(L-lactide)/poly(D-lactide) stereocomplex" , Polymer, vol. 44, p. 5635, 2003.
[49] Y. L. Zhao, Q. Cai, X. T. Shuai, J. Z. Bei, C. F. Chen, F. Xi, " Synthesis and thermal properties of novel star-shaped poly(L-lactide)s with starburst PAMAM–OH dendrimer macroinitiator" , Polymer, vol. 43, p. 5819, 2002.
[50] E. S. Kim, B. C. Kim, S. H. Kim, " Structural effect of linear and star-shaped poly(L-lactic acid) on physical properties" , Polymer Science, Part B: Polymer Physics, vol. 42, p. 939, 2004.
[51] H. Liu, F. Chen, B. Liu, G. Estep, J. Zhang, " Super Toughened Poly(lactic acid) Ternary Blends by Simultaneous Dynamic Vulcanization and Interfacial Compatibilization" , Macromolecules, vol. 43, p. 6058, 2010.
[52] L. Jiang, M. P. Wolcott, J. Zhang, " Study of Biodegradable Polylactide/Poly(butylene adipate-co-terephthalate) Blends" , Biomacromolecules, vol. 7, p. 199, 2006.
[53] J. Zeng, A. Aigner, F. Czubayko, T. Kissel, J. H. Wendorff, A. Greiner, " Poly(vinyl alcohol) nanofibers by electrospinning as a protein delivery system and the retardation of enzyme release by additional polymer coatings" , Biomacromolecules, vol. 6, pp. 1484-1488, 2005.
[54] H. Tsuji, Y. Ikada, S. H. Hyon, Y. Kimura, T. J. Kitao, Stereocomplex formation between enantiomeric poly(lactic acid). VIII. Complex fibers spun from mixed solution of poly(D-lactic acid) and poly(L-lactic acid), Applied Polymer Science, vol. 51, p. 337, 1994.
[55] C. H. Ho, C. H. Wang, C. I. Lin, Y. D. Lee, " Synthesis and characterization of TPO-PLA copolymer and its behavior as compatibilizer for PLA/TPO blends", Polymer, vol. 49, p. 3902-3910, 2008.
[56] J. Puiggali, Y. Ikada, H. Tsuji, L. Cartier, T. Okihara, B. Lotz, " The frustrated structure of poly(l-lactide) " , Polymer, vol. 41, pp. 8921-8930, 2000.
[57] J. M. Zhang, Y. X. Duan, H. Sato, H. Tsuji, I. Noda, S. K. Yan, Y. Ozaki, " Crystal Modifications and Thermal Behavior of Poly(L-lactic acid) Revealed by Infrared Spectroscopy" , Macromolecules, vol. 38, pp. 8012-8021, 2005.
[58] J. M. Zhang, K. Tashiro, H. Tsuji, A. J. Domb, " Disorder-to-Order Phase Transition and Multiple Melting Behavior of Poly(L-lactide) Investigated by Simultaneous Measurements of WAXD and DSC" , Macromolecules, vol. 41, pp. 1352-1357, 2008.
[59] J. M. Zhang, K. Tashiro, H. Tsuji, A. J. Domb, " Investigation of Phase Transitional Behavior of Poly(L-lactide)/Poly(D-lactide) Blend Used to Prepare the Highly-Oriented Stereocomplex" , Macromolecules, vol. 40, pp. 1049-1054, 2007.
[60] W. Hoogsten, A. R. Postema, A. J. Pennings, G. t. Brinke, P. Zugenmair, " Crystal structure, conformation and morphology of solution-spun poly(L-lactide) fibers" , Macromolecules, vol. 23, p. 634, 1990.
[61] S. Sasaki, T. Asakura, " Helix Distortion and Crystal Structure of the α-Form of Poly(L-lactide) " , Macromolecules, vol. 36, p. 8385, 2003.
[62] H. Tsuji, " Polylactides" , Biopolymers, vol.4, pp. 129-177, 2002.
[63] H. Tsuji, Y. Ikada, " Stereocomplex formation between enantiomeric poly(lactic acids). 9. Stereocomplexation from the melt" , Macromolecules, vol. 26, p. 6918, 1993.
[64] J. J. Kolstad, "Crystallization kinetics of poly(L-lactide-co-meso-lactide) " , Applied Polymer Science, vol. 62, p. 1079, 1996.
[65] R. E. Drumright, P. R. Gruber, D. E. Henton, " Polylactic Acid Technology" , Advanced Materials, vol. 12, p. 1841, 2000.
[66] J. Zhang, K. Tashiro, H. Tsuji, A. J. Domb, Disorder-to-Order Phase Transition and Multiple Melting Behavior of Poly(L-lactide) Investigated by Simultaneous Measurements of WAXD and DSC, Macromolecules, Vol. 41, p.1354, 2008.
[67] J. B. Snook, M.Sc. Thesis, Dissertation of Michigan State University, East Lansing, p. 130, 1994.
[68] X. Zhang, U. P. Wyss, D. Pichora, M. F. A. Goosen, " An Investigation of Poly(lactic acid) Degradation" , Bioactive and Compatible Polymers, vol. 9, p. 80, 1994.
[69] M. H. Hartmann, N. Whiteman, " TAPPI Polymers, Laminations, &; Coatings Conference" , Chicago, IL, United States, pp. 467-474, 2000.
[70] 黃士哲, "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," 元智大學碩士論文, pp. 27, 1998