臺灣博碩士論文加值系統

本研究主要以不同比例的聚(3-羥基丁酸酯-co-3-羥基戊酸酯) Poly(3-hydroxybutyrate-co-3-hydroxyvalerate, PHBV)和聚乙二醇 Poly(ethylene glycol, PEG)進行共聚形成PHEG嵌段共聚物，探討嵌段共聚物中同心圓球晶的結晶形態與微結構的變化。
實驗以微差掃描熱分析儀(Differential Scanning Calorimetre, DSC)觀察嵌段共聚物結晶與熔融行為，以可加熱式偏光顯微鏡(Hot Stage Polarizing Microscope, HSPM)觀察嵌段共聚物的同心圓球晶形態，再以原位傅立葉轉換紅外光譜儀(In-situ Fourier Transform Infrared Spectrometer, In-situ FTIR)觀察嵌段共聚物結晶過程的組型變化，最後以小角 X 光散射儀(Small angle x-ray Scattering, SAXS)觀察嵌段共聚物之長週期與微結構的變化。
根據DSC與HSPM結果顯示，PHEG嵌段共聚物中有二個結晶放熱峰，高溫的結晶峰屬於PHBV嵌段，低溫的結晶峰對應PEG嵌段。在HSPM觀察發現PHEG2000、PHEG4000和PHEG6000中皆有觀察到同心圓球晶結構。PHEG4000在35 ℃下先形成PHBV嵌段的結晶結構，接著隨持溫時間的增加，PEG嵌段有可能在PHBV結晶結構之間的有限空間下形成結晶。而PEG嵌段分子鏈受到PHBV嵌段先形成的結晶結構的影響，較容易在PHBV球晶的中心處形成晶核，因此形成同心圓球晶。各嵌段的球晶半徑成長速率會受到結晶環境的影響，因此在未受限環境下的PHBV嵌段的結晶速率大於受限環境下的PHBV嵌段的結晶速率，而受限環境下的PEG嵌段的結晶速率大於未受限環境下的PEG嵌段的結晶速率。
在FTIR和SAXS結果顯示，在緩慢降溫至70 ℃時PHBV嵌段的分子鏈先形成結晶的組型結構，而降溫到35 ℃後PEG嵌段的分子鏈開始排列形成結晶的組型結構。在SAXS實驗中先形成的PHBV結晶結構作為PEG嵌段的模板，接著再升溫到70 ℃時，PEG嵌段形成的結晶結構被熔融，長週期(L)與非晶層厚度(la)明顯的增加，由此可推測熔融後的PEG嵌段存在於PHBV的結晶層之間。

Crystalline-crystalline Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Poly(ethylene glycol) block copolymers (PHEGs) were synthesized form PHBV2000 and PEG with different number-average molecular weights. This study focused on the microstructure of the concentric spherulite of double crystalline block copolymers.
The crystallization and melting behaviors were studied by a differential scanning calorimeter (DSC). The concentric spherulite morphology was observed with a hot stage polarizing microscope (HSPM). The conformation were investigated by an In-situ Fourier transform infrared spectrometer (In-situ FTIR). The microstructure was probed by small angle x-ray scattering (SAXS).
Based on DSC and HSPM studies, two crystallization peaks were observed in the PHEGs during the cooling process, where the high temperature crystallization peak related to the PHBV block and low temperature crystallization peak corresponded to the PEG block, respectively. There was a crystallization exothermic peak in PHEG copolymer under isothermal crystallization conditions. It indicated that PHBV block and PEG block crystallized in the same isothermal crystallization condition. In addition, the concentric spherulite morphology of the PHEG2000, PHEG4000, and PHEG6000 were observed using HSPM. The spherulite growth in the PHEG4000 of PHBV block formed first at 35 ℃, then the PEG block crystallized within confined space between the formerly formed PHBV crystal lamellae. The most stretched PEG chain at the center of the PHBV spherulite may nucleate easily under the enough crystallization time, resulting in the formation of the concentric spherulite. The spherulite growth rate of individual spherulites from the PEG block and PHBV block in PHEGs depends on the crystallization environment. However, the growth rate of the unrestricted PHBV block was faster than that of the confined PHBV block and the growth rate of the confined PEG block was faster than that of the unrestricted PEG block.
FTIR and SAXS results showed that the PHBV chains were observed in preferred conformations in the crystalline states during the cooling process at 70 ℃, and then continuously adjusted conformational transition in PEG chain were rearranged to form the crystalline during the isothermal crystallization at 35 ℃. SAXS result, the first growth PHBV spherulite acted as the template for the spherulite growth of the PEG block. In addition, we heated to 70 ℃ for melting the PEG block. The long period (L) and amorphous thickness (la) increased. It was possible that the melting of the PEG block existing in the PHBV crystal lamellae.

第一章 緒論 1
1.1前言 1
1.2雙結晶型嵌段共聚物 2
1.3聚3-羥基丁酸酯-co–3-羥基戊酸酯(Poly(3-hydroxybutyrate-co-3-hydroxyvalerate, PHBV) 5
1.4聚乙二醇(Poly ethylene glycol, PEG) 6
1.5研究動機與目的 7
第二章 實驗 8
2.1實驗流程 8
2.2實驗材料 9
2.3 實驗設備 10
2.3.1可加熱式偏光顯微鏡(Hot Stage Polarizing Microscope, HSPM ) 10
2.3.2微差掃描熱分析儀(Differential Scanning Calorimetre, DSC) 10
2.3.3原位傅立葉轉換紅外光譜儀 (In-situ Fourier Transform Infared, In-situ FTIR) 10
2.3.4 小角X光散射儀 (Small Angle X-ray Scattering System, SAXS) 10
2.4 實驗方法 11
2.4.1 HSPM等溫結晶實驗條件 11
2.4.2傅立葉轉換紅外光譜樣品製備與實驗 12
2.4.3 DSC非等溫結晶實驗 12
2.4.4 SAXS實驗條件 14
第三章 結果與討論 20
3.1 熱性質分析 20
3.1.1 PHEG嵌段共聚物之熱性質分析 20
3.1.2小結 24
3.2 球晶形態分析 25
3.2.1球晶形態觀察 25
3.2.2 同心圓球晶的生長過程 27
3.2.3小結 33
3.3 PHEG嵌段共聚物之特徵吸收峰 34
3.3.1 PHEG嵌段共聚物特徵吸收峰分析 34
3.3.2小結 39
3.4 結晶微結構分析 40
3.4.1 PHEG嵌段共聚物SAXS結晶微結構分析 40
3.4.2小結 48
第四章 結論 49
參考文獻 51

1.L.H. Sperling, Introduction to physical polymer science, pp.25-77, 1992.
2.F. S. Bates, Polymer-Polymer Phase Behavior, Science, 251, pp.898-905, 1991.
3.U. Gedde, Polymer Physics., pp.5, 1995.
4.C. Chen, S. Peng, B. Fei, Y. Zhuang, L. Dong, Z. Feng, S. Chen, H. Xia, Synthesis and Characterization of Maleated Poly(3-hydroxybutyrate), Journal of Applied Polymer Science, 88, 3, pp.659-668, 2003.
5.R. M. Macrae, J. F. Wilkison, Poly-β-hyroxybutyrate Metabolism in Washed Suspensions of Bacillus cereus and Bacillus megaterium, Journal of General Microbiology, 19, pp.210-222, 1958.
6.J. S. Yoon, S. H. Oh, M. N. Kim, Compatibility of poly(3-hydroxybutyrate)/poly(ethylene-co-vinyl acetate) blends, Polymer, 39, 12, pp.2479-2487, 1998.
7.Q. S. Liu, M. F. Zhu, W. H. Wu, Z. Y. Qin, Reducing the formation of six-membered ring ester during thermal degradation of biodegradable PHBV to enhance its thermal stability, Polymer Degradation and Stability, 94, pp.18-24, 2009.
8.L. Zhang, C. Xiong, X. Deng, Miscibility, crystallization and morphology of poly(P-hydroxybutyrate)/poly(d,l-lactide) blends, Polymer, 37, 2, pp.235-241, 1996.
9.T. L. Bluhm, G. K. Hamer, R. H. Marchessault, Isodimorphism in Bacterial Poly (β-hydroxybutyrate-co-β- hydroxyvalerate), Macromolecules, 19, pp.2871-2876, 1986.
10.M. Kunioka, A. Tamaki, Y. Doi, Crystalline and Thermal Properties of Bacterial Copolyesters: Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Poly(3- hydroxybutyrate-co-4-hydroxybutyrate), Macromolecules, 22, pp.694-697,1989.
11.M. Scandola, G. Ceccorulli, M. Pizzoli, M. Gazzano, Study of the Crystal Phase and Crystallization Rate of Bacterial Poly(3- hydroxybutyrate-co-3-hydroxyvalerate), Macromolecules, 25, pp.1405-1410, 1992.
12.H. Mitomo, N. Morishita, Y. Doi, Structuralchanges of poly(3-hydro xybutyrate-co-3-hydroxyvaIerate)fractionated with acetone-water solution, Polymer, 36, 13, pp.2573-2578, 1995.
13.H. Mitomo, N. Morishita, Y. Doi, Composition Range of Crystal Phase Transition of Isodimorphism in Poly(3-hydroxybutyrate-co- thydroxyvalerate), Macromolecules, 26, pp.5809-5811,1993.
14.X. Li., X. J. Loh, K. Wang, C. He, J. Li, Poly(ester urethane)s Consisting of Poly[(R)-3-hydroxybutyrate] and Poly(ethylene glycol) as Candidate Biomaterials: Characterization and Mechanical Property Study, Biomacromolecules, 6, pp.2740 -2747, 2005.
15.H. Y. Tian, C. Deng, H. Lin, J. Sun, M. Deng, X. Chen, X. Jing, Biodegradable cationic PEG–PEI–PBLG hyperbranched block copolymer: synthesis and micelle characterization, Biomaterials, 26, pp.4209-4217, 2005.
16.X. Li, K. L. Liu, J. Li, E. P. S. Tan, L. M. Chen, C. T. Lim, S. H. Goh, Synthesis, Characterization, and Morphology Studies of Biodegradable Amphiphilic Poly[(R)-3-hydroxybutyrate]-alt-Poly(ethylene glycol) Multiblock Copolymers, Biomacromolecules, 7,pp.3112 - 3119, 2006.
17.X. J. Loh, K. K. Tan, X. Li, J. Li, The in vitro hydrolysis of poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol), Biomaterials, 27, pp.1841-1850, 2006.
18.Y. S. Wang, S. Youngster, M. Grace, J. Bausch, R. Bordens, D. F. Wyss, Structural and biological characterization of pegylated recombinant interferon alpha-2b and its therapeutic implications, Advanced Drug Delivery Reviews, 54, pp.547–570, 2002.
19.J. Sun, Z. Hong, L. Yang, Z. Tang, X. Chen, X. Jing, Study on crystalline morphology of poly(L-lactide)-poly(ethylene glycol) diblock copolymer, Polymer, 45, pp.5969-5977, 2004.
20.J. Yang, T. Zhao, L. Liu, Y. Zhou, G. Li, E. Zhou, X. Chen, Isothermal Crystallization Behavior of the Poly(L-lactide) Block in Poly(L-lactide)-Poly(ethylene glycol) Diblock Copolymers: Influence of the PEG Block as a Diluted Solvent, Polymer Journal, 38, pp.1251-1257, 2006.
21.C. He, J. Sun, C. Deng, T. Zhao, M. Deng, X. Chen, X. Jing, Study of the Synthesis, Crystallization, and Morphology of Poly(ethylene glycol) -Poly(ε-caprolactone) Diblock Copolymers, Biomacromolecules, 5, pp.2042 -2047, 2004.
22.C. He, J. Sun, C. Deng, T. Zhao, M. Deng, X. Chen, X. Jing, Formation of a Unique Crystal Morphology for the Poly(ethylene glycol)-Poly(ε-caprolactone) Diblock Copolymer, Biomacromolecules, 7, pp.252-258 , 2006.
23.J. Sun, C. He, X. Zhuang, X. Jing, X. Chen, The crystallization behavior of poly(ethylene glycol)-poly(ε-caprolactone) diblock copolymers with asymmetric block compositions, Journal of Polymer Research , 18, pp.2161-2168, 2011.
24.Q. Liu, T. W. Shyr, C. H. Tung, M. Zhu, B. Deng, Peculiar Spherulitic Morphologies and Melting Behavior of Block Copolymer Containing Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Poly(ε- caprolactone) Units, Macromolecular Research, 19, 12, pp.1220-1223, 2011.
25.Q. Liu, B. Deng, C. H. Tung, M. Zhu, T. W. Shyr, Nonisothermal Crystallization Kinetics of Poly(ε-caprolactone) Blocks in Double Crystalline Triblock Copolymers Containing Poly(3-hydroxy- butyrate- co-3-hydroxyvalerate) and Poly(ε-caprolactone) Units, Journal of Polymer Science: Part B: Polymer Physics, 48, pp.2288-2295, 2010.
26.Q. Liu, B. Deng, C. H. Tung, M. Zhu, T. W. Shyr, Block Copolymers Containing Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) and Poly (ε-caprolactone) Units: Synthesis, Characterization and Thermal Degradation, Fibers and Polymers, 12, 7, pp.848-856, 2011.
27.T. Shiomi, K. Imai, K. Takenaka, H. Takeshita, H. Hayashi, Y. Tezuka, Appearance of double spherulites like concentric circles for poly(ε-caprolactone) -block- poly(ethylene glycol) -block- poly(ε-caprolactone), Polymer, 42, pp.3233-3239, 2001.
28.T. Shiomi, H. Takeshita, K. Fukumoto, T. Ohnishi, T. Ohkubo, M. Miya, K. Takenaka, Formation of lamellar structure by competition in crystallization of both components for crystalline-crystalline block copolymers, Polymer, 47, pp.8210-8218, 2006.
29.I. W. Hamley, V. Castelletto, R. V. Castillo, A. J. Muller, C. M. Martin, E. Pollet, Ph. Dubois, Crystallization in Poly(L-lactide)-b-poly(ε-caprolactone) Double Crystalline Diblock Copolymers: A Study Using X-ray Scattering, Differential Scanning Calorimetry, and Polarized Optical Microscopy, Macromolecules, 38, pp.463-472, 2005.
30.I. W. Hamley, P. Parras, V. Castelletto, R. V. Castillo, A. J. Muller, E. Pollet, P. Dubois, C. M. Martin, Melt Structure and its Transformation by Sequential Crystallization of the Two Blocks within Poly(L -lactide)-block-Poly(ε-caprolactone) Double Crystalline Diblock Copolymers, Macromolecular Chemistry and Physics, 207, pp.941-953, 2006.
31.J. K. Kim, D. J. Park, M. S. Lee, K. J. Ihn, Synthesis and crystallization behavior of poly(L-lactide)-block- poly(ε-caprolactone) copolymer, Polymer, 42, pp.7429-7441, 2001.
32.C. C. Han, J. Yang, Y. Liang, J. Luo, C. Zhao, Multilength Scale Studies of the Confined Crystallization in Poly(L-lactide)-block -Poly(ethylene glycol) Copolymer, Macromolecules, 45, pp.4254-4261,2012.
33.Q. Liu, M. Zhu, Y. Chen, Synthesis and characterization of multi-block copolymers containing poly [(3-hydroxybutyrate)-co- (3-hydroxyvalerate)] and poly(ethylene glycol), Polymer International, 59, pp.842-850,2010.
34.Z. Shen, W. Zhu, W. Xie, X. Tong, Amphiphilic biodegradable poly(CL-b-PEG-b-CL) triblock copolymers prepared by novel rare earth complex: Synthesis and crystallization properties, European Polymer Journal, 43 , pp.3522-3530, 2007.
35.L.H. Sperling, Introduction to Physical Polymer Science, pp.223-224,1992.
36.P. Cebe, Scattering from Polymers., pp.12-18,1999.
37.W. J. Ruland, Journal of Applied Crystallography, 4, 70, 1971.
38.G. Porod, Z. Koll, 124, 83, 1951.
39.G. Porod, Z. Koll, 125, 51, 1952.
40.G. Porod, Z. Koll, 125, 108 , 1952.
41.P. Debye, A. M. Bueche, Journal of Applied Physics, 20, 518, 1949.
42.B. Bogdanov, A. Vidts, E. Schacht, H. Berghmans, Isothermal Crystallization of Poly(ε-caprolactone - ethylene glycol) Block Copolymers, Macromolecules, 32, pp.726-731, 1999.
43.H. Matsuura, T. Miyazawa, Vibrational Analysis of Molten Poly (ethylene glycol), Journal of Polymer Science: PartA-2, 7, pp.1735-1744, 1969.
44.T. Miyazawa, K. Fukushima, Y. Ideguchi, Molecular Vibrations and Structure of High Polymers III Polarized Infrared Spectra, Normal Vibrations, and Helical Conformation of Polyethylene Glycol, Journal of Chemical Physics, 37, pp.2764-2776, 1962.
45.R. M. Kannan, P. Kolhe, Improvement in Ductility of Chitosan through Blending and Copolymerization with PEG: FTIR Investigation of Molecular Interactions, Biomacromolecules, 4, pp.173-180, 2003.
46.P. Harder, M. Grunze, R. Dahint, G. M. Whitesides, P. E. Laibinis, Molecular Conformation in Oligo(ethylene glycol)- Terminated Self-Assembled Monolayers on Gold and Silver Surfaces Determines Their Ability To Resist Protein Adsorption, Journal of Physical Chemistry B, 102, pp.426-436, 1998.
47.J. Zhang, H. Sato, I. Noda, Y. Ozaki, Conformation Rearrangement and Molecular Dynamics of Poly(3-hydroxybutyrate) during the Melt-Crystallization Process Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy, Macromolecules, 38, pp.4274-4281, 2005.
48.A. Padermshoke, Y. Katsumoto, H. Sato, S. Ekgasit, I. Noda, Y. Ozaki, Melting behavior of poly(3-hydroxybutyrate) investigated by two-dimensional infrared correlation spectroscopy, Spectrochimica Acta Part A , 61, pp.541-550, 2005.
49.J. Li, M. F. Lai, J. J. Liu, Effect of Poly(propylene carbonate) on the Crystallization and Melting Behavior of Poly(β-hydroxybutyrate-co-β- hydroxyvalerate), Journal of Applied Polymer Science, Vol. 92, pp.2514-2521, 2004.
50.J. Xu, B. H. Guo, R. Yang, Q. Wu, G. Q. Chen, Z. M. Zhang, In situ FTIR study on melting and crystallization of polyhydroxyalkanoates, Polymer, 43, pp.6893-6899 , 2002.
51.J.Zhang, Y. Duan, H. Sato, H. Tsuji, I. Noda, S. Yan, Y. Ozaki, Crystal Modifications and Thermal Behavior of Poly(L-lactic acid) Revealed by Infrared Spectroscopy, Macromolecules, 38, pp.8012-8021, 2005.
52.M. Radjabian, M. H. Kish, N. Mohammadi, Characterization of Poly(lactic acid) Multifilament Yarns. I. The Structure and Thermal Behavior, Journal of Applied Polymer Science, 117, pp.1516-1525, 2010.
53.J. Zhang, H. Tsuji, I. Noda, Y. Ozaki, Structural Changes and Crystallization Dynamics of Poly(L-lactide) during the Cold-Crystallization Process Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy, Macromolecules, 37, pp.6433-6439, 2004.
54.J. Zhang, H. Sato, H. Tsuji, I. Noda, Y. Ozaki, Infrared Spectroscopic Study of CH3‧‧O=C Interaction during Poly(L-lactide)/Poly(D-lactide) Stereocomplex Formation, Macromolecules, 38, pp.1822-1828, 2005.
55.H.L. Chen, H. L, Chen, J. S. Lin, Crystallization induced microstructure of crystalline/crystalline poly(vinylidenefluoride)/ poly(3-hydroxybutyrate) blends probed by small angle X-ray scatteringpolymer, 42, pp.5749-5754,2001.
56.T. W. Shyr, C. H. Tung, W. S. Cheng, S. D. Jiang, S. K. Yan, Z. H. Gan, The conformational changes, crystal structure and melting behavior of poly(ethylene/trimethylene terephthalate) copolyesters, Polymer International, 61, pp.780-787, 2012.