博碩士論文 84321043 詳細資訊




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姓名 曾益民(I-Min Tseng)  查詢紙本館藏   畢業系所 化學工程與材料工程學系
論文名稱 聚芳香羧酸酯之合成及性質研究
(Synthesis and Characterization of Aromatic Polyester)
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摘要(中) 聚對苯二甲酸二乙酯(PET,polyethylene terephthalate)具有高機械強度、耐化學溶劑等特性。然而PET熔點相當高,需要較高的加工溫度。聚對苯二甲酸二丙酯(PPT,polypropylene terephthalate)的熔點比PET低,而且化學結構與PET相近,與PET的相容性佳。若以PPT改質PET形成PPT/PET共聚酯以降低PET的熔點,將有助於改善PET的加工性。
本研究探討不同合成反應條件及反應進料組成對PPT/PET共聚酯結構與性質的影響。熱分析結果顯示,不同反應條件與組成所得到的共聚酯均為均勻相。以13C-NMR分析順序結構(sequence)分佈結果顯示共聚酯為random共聚酯。可能是酯交換反應使得共聚酯的分子結構排列趨向於形成random 共聚酯。以X-射線繞射分析結果顯示PPT/PET共聚酯的結晶結構大致可以分為三類,當PPT/PET共聚酯的組成接近PET時,其結晶結構與PET均聚酯的結晶結構相似;當組成接近PPT時,其結晶結構與PPT均聚酯的結晶結構相似;當PPT含量約為50 mol%時,PPT/PET共聚酯的結晶結構與PET均聚酯及PPT均聚酯的結晶結構均完全不同。由微差掃描式熱分析儀(DSC, differential scanning calorimetry)分析結果顯示,當PPT/PET共聚酯的PPT含量在小於10 mol%或大於70 mol%範圍內時,PPT/PET共聚酯結晶速率明顯較快,PPT/PET共聚酯的玻璃轉移溫度(Tg )隨PPT含量增加而降低,熔點(Tm )則先降低至PPT含量約為50 mol%時再增加。
關鍵字(中) ★ 亂度參數
★ 芳香四級碳
★ 聚芳香羧酸酯
★ 順序結構
關鍵字(英) ★ randomness parameter
★ aromatic queternary carbon
★ Aromatic Polyester
★ sequence
論文目次 目錄
中文摘要i
英文摘要ii
目錄iii
表目錄v
圖目錄vii
第一章緒論
1.1 前言1
1.2 理論與文獻回顧3
1.2.1 聚酯的合成3
1.2.2 聚酯的結晶結構5
1.2.3 共聚酯的順序結構(sequence)8
1.2.4 聚合體的Tm、Tg9
第二章 實驗
2.1 化學試藥13
2.2 儀器設備14
2.3 實驗方法15
2.3.1 聚酯合成方法16
2.3.2 極限黏度及分子量分析方法19
2.3.3 共聚酯的組成及順序結構分析20
2.3.4 聚酯的熱學性質分析22
(1)熱重量分析(TGA)測定22
(2)動態機械分析(DMA)測定22
(3)微差掃描熱分析(DSC)測定22
2.3.5 共聚酯的結晶結構分析23
第三章 結果與討論
3.1 聚酯的合成24
3.1.1 PPT均聚酯的合成24
3.1.2 PET均聚酯的合成26
3.1.3 PPT/PET共聚酯的合成27
3.2 PPT/PET共聚酯的組成及順序結構(sequence)28
3.2.1 共聚酯的鑑定組成29
3.2.2 PPT/PET共聚酯的順序結構32
3.3 聚酯的熱分析34
3.3.1 熱穩定性分析35
3.3.2 動態機械分析36
3.3.3 聚酯的結晶性與Tg、Tm 36
3.4 PPT/PET共聚酯結晶結構分析41
3.4.1 回火(annealing)對結晶的影響41
34.2 共聚酯結晶結構分類41
3.4.3 共聚酯組成與結晶結構43
第四章 結論45
第五章 參考文獻46
表目錄
表3-1PPT均聚酯的合成反應條件及極限黏度49
表3-2PPT均聚酯的極限黏度與分子量50
表3-3PPT均聚酯的極限黏度實驗值及計算值比較51
表3-4不同方法合成共聚酯的反應條件、極限黏度及分子量52
表3-5不同組成PPT/PET共聚酯合成反應條件及極限黏度53
表3-6PPT/PET共聚酯的極限黏度與分子量54
表3-7共聚酯的1H-NMR頻譜圖的化學位移(chemical shift)55
表3-8不同合成方法的PPT/PET共聚酯的進料組成及1H-NMR分析組成56
表3-9PPT/PET共聚酯的進料組成及1H-NMR分析組成57
表3-10共聚酯的13C-NMR頻譜圖的化學位移58
表3-11芳香四級碳的13C-NMR頻譜圖的化學位移59
表3-12不同合成方法共聚酯的芳香四級碳的順序結構機率(triad sequence probability)60
表3-13不同合成方法共聚酯的組成,亂度參數值,數量平均順序結構長度(Number-Average Sequence Lengths)61
表3-14芳香四級碳的順序結構機率62
表3-15共聚酯的組成,亂度參數值,數量平均順序結構長度63
表3-16PPT/PET摻合的13C-NMR,1H-NMR分析組成比較64
表3-17PPT均聚酯的DSC熱分析性質Tg, Tm,Tch及Tcc 65
表3-18不同合成方法的PPT/PET共聚酯的Tg, Tm66
表3-19共聚酯的DSC熱分析性質Tg, Tm, Tch, Tcc及t1/267
圖目錄
圖1-1聚合體晶體中分子排列示意圖68
圖1-2PPT分子單晶的b-c平面結構圖69
圖1-3PET分子單晶結構圖70
圖1-4Melting points, solubility temperature, and second-order transition temperatures of poly(methylene terephthalate)71
圖2-1PPT、PET聚酯的結構單元、重複單元及其代表符號72
圖2-2PPT/PET共聚酯的順序結構單元及其代表符號73
圖2-3PPT均聚酯C1的hsp/c及(lnhr)/c對濃度c作圖74
圖2-4PPT/PET共聚酯M4的GPC分子量分佈圖75
圖2-5PPT均聚酯C1的DSC曲線圖76
圖2-6PET均聚酯C9的DSC曲線圖77
圖3-1PPT均聚酯極限黏度與聚縮合反應時間關係圖78
圖3-2PPT均聚酯的極限黏度與重量平均分子量關係圖79
圖3-3PPT均聚酯的極限黏度與數量平均分子量關係圖80
圖3-4PET均聚酯C9的400MHz, 1H-NMR頻譜圖81
圖3-5PPT均聚酯C1的400MHz, 1H-NMR頻譜圖82
圖3-6PPT與PET摻合的1H-NMR頻譜圖83
圖3-7PPT/PET共聚酯M4的400MHz, 1H-NMR頻譜圖84
圖3-8PPT/PET共聚酯的組成對進料組成圖85
圖3-9PET均聚酯C9的100MHz, 13C-NMR頻譜圖86
圖3-10PPT均聚酯C1的100MHz, 13C-NMR頻譜圖87
圖3-11PPT與PET摻合(50/50, w/w)的13C-NMR頻譜圖88
圖3-12PPT/PET共聚酯M4的100MHz, 13C-NMR頻譜圖89
圖3-13M1、M2、M3、M4的芳香四級碳的13C-NMR頻譜圖90
圖3-14C2、C3、C5的芳香四級碳的 13C-NMR頻譜圖91
圖3-15C6、C7、C8的芳香四級碳的13C-NMR頻譜圖92
圖3.16PPT、PPT/PET共聚酯、PET的熱重量損失圖93
圖3-17PPT、PET、PPT/PET共聚酯的DMA曲線圖94
圖3-18PPT、PET、PPT/PET共聚酯的DSC的Tg,及Tm曲線圖95
圖3-19PPT、PET、PPT/PET共聚酯的DSC的Tcc 曲線圖96
圖3-20PPT均聚酯的Tg及Tm對極限黏度的分佈圖97
圖3-21PPT/PET共聚酯的DSC熱分析Tg對組成的分佈圖98
圖3-22PPT/PET共聚酯的DSC熱分析Tm 對組成的分佈圖99
圖3-23PPT/PET共聚酯的Tm對共聚酯的組成的分佈比較圖100
圖3-24M4回火(annealing)處理前後的XRD繞射光譜101
圖3-25C5,PPT與PET摻合,C1,C9的XRD繞射光譜102
圖3-26C9,C8,C7,C6的XRD繞射光譜103
圖3-27C1,C2的XRD繞射光譜104
圖3-28C5,M4,C3的XRD繞射光譜105
參考文獻 1.Tseng, I-Min, Huang, Jih-Chen, Juang, Chyuan, “Processes for 1,3-Propanediol and Poly (propylene terephthalate) Manufacture”, Chemical Information Monthly, Vol.12, No.6, Jun., 1998
2.Whinfield, John. Rex, and Dickson, James Tennant, “Fibers from Glycol Terephthalate Polymers”, GB 578079, June 14, 1946
3.Whinfield, John Rex, and Dickson, James Tennant, “Polymeric Linear Terephthalic Esters”, Du Pont de Nemours, E. I., & Co., U.S. Patent 2465319, 1949
4.“Shell Enters the Carpet Industry: New Polymer Has Characteristics of Nylon, Polyester”, Floor Covering News, Vol. 10, No. 5, May 22/29, 1995
5.Traub, H. L., Hirt, P., Herlinger H., Oppermann W.,”Synthesis and properties of fiber-grade poly(trimethylene terephthalate)”, Die Angewandte Makromolekulare Chemie 230, Nr. 4055, pp179-187, 1995
6.Lin, Chen-Chong and Baliga, Satish, “A Study on the Polycondensation of Bis-Hydroxyethyl Terephthalate”, Journal of Appied Polymer Science, Vol. 31, pp2483-2489, 1986
7.Ravindranath, K., and Mashelkar, R. A., “Polyethylene Terephthalate-I. Chemistry, Thermodynamics and Transport Properties”, Chemical Engineering Science, Vol. 41, No 9, pp2197-2214, 1986
8.Besnoin, J.-M., and Choi, K. Y., “Identification and Characterization of Reaction Byproducts in the Polymerization of Polyethylene Terephthalate”, Rev. Macromol. Chem.Phys., C29, (1), pp55-81, 1989
9.Kemkes, J. F., “Direct Esterification of Terephthalic Acid with Ethylene Glycol under Atmospheric Pessure”, Journal of Polymer Science, Part C, Vol.22, Pt. 2, pp713-720, 1967
10.Price, John A., Carlson, Otto K., “Group I-A Metal Manganites, Manganates, and Cobaltites as Polyester Polycondensation Catalysts”, FMC Corp., U.S.Patent 3475380, 1969
11.Price, John A., Carter, Mary E., “Polyethylene Terephthalate by Direct Esterification in the Presence of a Metal Citrate as a Direct Esterification Catalytic Additive”, FMC Corp., U.S.Patent 3475381, 1969
12.Koono, Mitsuo, Okamoto, Toshio, Kimura, Yoshio, Kitamura, Kazuyuki, “Polyesters”, Asahi Chemical Industry Co. Ltd., Japan Kokai, JP 47033190, 1972
13.Ikeuchi, Hiroyuki, Kamada, Katsuma, Okada, Katsuhiko, Tanaka, Michihiko, Kitagawa, Hideji, “Polyesters with Good Whiteness”, Toray Industries Inc., Japan Kokai, JP 48074596, 1973
14.Okada, Katsuhiko, Tanaka, Michihika, Kitagawa, Hideji, “Aromatic Dicarboxylic Acid Esters”, Toray Industries Inc., Japan. Kokai, JP 48068539, 1973
15.Rebhan, Joerg, Matthies, Hans G., “Continuous Production of Linear Polyesters”, BASF A.-G., Ger., Ger. Offen., DE 2449162, 1976
16.Kushimoto, Toshihiro, Ozawa, Yoshimichi, Yoshikawa, Etsuo, “Polyesters”, Kanebo, Ltd., Japan, Kokoritsu Gosen Gijutsu Kenyu Kumiai, Jpn. Kokai Tokkyo Koho, JP 62072718, 1987
17.Kushimoto, Toshihiro, Ozawa, Yoshimichi, Izawa, Nobuo, “Process for Producing Polyesters Using a Niobium Compound as a Catalyst”, Kanebo, Ltd., Japan; Research Assoc. for Synthetic Fiber Technology, EP 287840, 1988
18.Maurer, Charles J., “Process for Preparing Oligomeric Glycol Esters of Dicarboxylic Acids”, Celanese Corp., USA, U.S.Patant 4670580, 1987
19.Traub, H. L., Hirt, P., Herlinger, H., “Mechanical Properties of Fibers Made of Polytrimethylene Terephthalate”, Chemical Fibers International (CFI), Vol. 45, April, 1995
20.Wunderlich, Bernhard, “Macromolecular physics”, Vol, 1, Academic Press, pp184, 1973
21.Cullity, B. D., “Elements of X-Ray Diffraction”, Addision-Wesley Publishing Company, Inc., second edition, pp35, 1977
22.Balta-Calleja, F. J., Vonk, C. G., “X-Ray Scattering of Synthetic Polymers”, Elesevier, Polymer Science Library 8, pp19, 1989
23.Suzie, Poulin-Dandurand, Perez, Swrge, Revol, Jean-Francois, and Brisse, Francois, ”The crystal structure of poly(trimethylene terephthalate) by X-ray and electron diffraction”, Polymer, Vol 20, pp419-426, April, 1979
24.Desborough, I. J., Hall, I. H., and Neisser, J. Z., ”The structure of poly(trimethylene terephthalate)”, Polymer, Vol 20, pp545-552, May, 1979
25.Moss, Barbara, and Dorset, Douglas L., “Refinement of Linear Polymer Crystal Structures Determined from Electron Diffraction Data”, Journal of Polymer Science: Polymer Physics Edition, Vol. 20, pp1789-1804, 1982
26.Dorset, Douglas L., and Moss, Barbara, “Electron Crystal Structure Analysis of Linear Polymers-An Appraisal”, Adv. Chem. Ser. 203, Polym. Charact., pp409-416, 1983
27.Fakirov, Stoyko, Fischer, Erhard W., and Schmidt, Gunter F., “Unit Cell Dimensions of Poly(ethylene terephthalate)”, Die Makromolekulare Chemie, Vol. 176, pp2459-2465, 1975
28.Kinoshita, Yukio, Nakamura, Ryoko, Kitano, Yukishige, Ashida, Tamaichi, “A Crystallographic Investigation on A High Crystalline Poly(ethylene Terephthalate)”, Polymer Preprints, Vol. 20, pp454-457, 1979
29.Lawton, E. L., and Ringwald, E. L., “Physical Constants of Poly(oxyethylene-oxyterephthaloyl) (Poly(ethylene terephthalate))”, Polymer Handbook, Edited by Brandrup, J., and Immergut, E. H., John Wiley & Sons, Third Edition
30.VanderHart, D. L., Bohm, G. G. A., and Mochel, V. D., “Inferences About Molecular Motion From Proton Decoupled 13C NMR Spectra of Solid Polymers”, Polymer Preprints, Vol.22, pp261-263, 1981
31.Yamashita Yuhiko, “Single Crystals of Poly(ethylene Terephthalate)” Journal of Polymer Science: Part A, Vol.3, pp81-92, 1965
32.Moore, R. A. F., and Peters, R. H., “Structure-property Relationships in Poly(tetramethylene Terephthalate)/poly(tetramethylene Isophthalate) Copolyesters. Part I: Glass-transition Temperatures”. Text. Res. J., Vol.49, No.11, pp623-631, 1979
33.Menczel, Jozsef, and Wunderlich, Bernhard, “Phase Transitions in Mesophase Macromolecules. I. Novel Behavior in the Vitrification of Poly(ethylene Terephthalate-co-p-Oxybenzoate)”, Journal of Polymer Science: Polymer Physics Edition, Vol. 18, pp1433-1438, 1980
34.Newmark, Richard A., “Sequence Distribution in Polyethylene/Tetramethylene Terephthalate Copolyesters by 13C-NMR”, Journal of Polymer Science: Polymer Chemistry Edition, Vol.18, pp559-563, 1980
35.Wunderlich, Bernhard, “Macromolecular Physics”, Academic Press, New York, Vol.3 Crystal Melting, Chapter 8, pp30, 1980
36.Flory, Paul J., “Thermodynamics of Crystallization in High Polymers. IV. A Theory of Crystalline States and Fusion in Polymers, Copolymers, and Their Mixtures with Diluents”, The Journal of Chemical Physics, Vol. 17, No.3, pp223-240, 1949
37.Meares, Patrick, “Polymers: Structure and Bulk Properities”, Van Nostrand Reinhold Company, London, Chapter 10, pp262, 1965
38.Balachandar, M., Balakrishnan, T., and Kothandaraman, H., “Thermal Properties of Random Copolyesters of PET and 3-and 3,5-Bromo-Substituted p-Hydroxybenzoic Acids II”, Journal of Polymer Science: Polymer Chemistry Edition, Vol.20, pp2624-2632, 1982
39.Smith, James G., Kibler, Charles J. and Sublett, Bobby J., “Preparation and Properties of Poly(methylene terephthalates)”, Journal of Polymer Science: Part A-1, Vol., 4, pp1851-1859, 1966
40.Ponnusamy, E., and Balakrishnan T., “Preparation and Characterization of Poly(ethylene/Trimethylene Terephthalate) Copolyesters”, J. Macromol. Sci-Chem., Vol.A22, No.3, pp.373-378, 1985
41.Miyagi, Arata., and Wunderlich, Bernhard, “Annealing during Polymerization of Crystalline Poly(ethylene Terephthalate)”, Journal of Polymer Science: Polymer Physics Edition, Vol.10, pp2085-2092, 1972
42.Lenz, Robert.W., and Schuler, Alan N., “Crystallization-induced Reactions of Copolymers. V. Important Reaction Variables in The Reorganization of Random to Block Copolyesters”, Journal of Polymer Science: Polymer Symposium, Vol.63, pp343-363, 1978
43.Jackson, John Brian, and Longman, G. W., “Crystallization of Poly(ethylene Terephthalate) and Related Copolymers”, Polymer, Vol.10, No.11, pp873-874, 1969
指導教授 蔣孝澈(A.S.T. Chiang) 審核日期 2000-7-12
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