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博碩士論文 etd-0630113-110136 詳細資訊
Title page for etd-0630113-110136
論文名稱
Title
等量不同單體之脂肪族無規共聚酯的結晶形態與模型
Crystal morphology and models of aliphatic random copolyesters with equal amounts of comonomers
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
101
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2013-07-19
繳交日期
Date of Submission
2013-07-30
關鍵字
Keywords
序列長度、共聚酯、顆粒狀、纓狀微束、共晶
copolyester, fringed-micelle, sequence length, granule-like, cocrystallization
統計
Statistics
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中文摘要
使用四異丙基鈦為觸媒,藉由酯化與聚縮合反應,合成含50%丁二酸2-甲基二丙酯之聚丁二酸二丁酯共聚酯(PBMPSu 50/50)、含50%丁二酸二丙酯之聚丁二酸二丁酯共聚酯(PBPSu 50/50)、含50%丁二酸二乙酯之聚丁二酸二丁酯共聚酯(PBESu 50/50)及含50%丁二酸二丙酯之聚丁二酸二乙酯共聚酯(PEPSu 50/50)。利用核磁共振分析儀(NMR)碳譜分析計算四種共聚酯的亂度值趨近於1.00及平均序列長度為2.0±0.1,而藉由微差式掃描熱卡計(DSC)分析材料結晶度為低於20%。以偏光顯微鏡(PLM)、穿透式電子顯微鏡(TEM)及原子力顯微鏡(AFM)觀察結晶形態。由PLM所觀察到的結果顯示出PBMPSu 50/50及PBESu 50/50呈現不具光性的顆粒狀結構晶體,而PBPSu 50/50則呈現尺寸較小的球晶形態,PEPSu 50/50顯示出負光性的球晶形態。藉由TEM觀察得到PBMPSu 50/50結晶形態為顆粒狀結構,而PBPSu 50/50則呈現短且薄的層狀結構。利用小角度X光散射(SAXS)及小角度光散射(SALS)來研究材料的微結構。由SAXS的一維關聯函數分析結果得到PBMPSu 50/50及PBESu 50/50只顯現一個最大值,這個現象表示結晶結構是呈現短程範圍有序。另外,由一維關聯函數分析得到PBPSu 50/50的層狀厚度為2.3 nm,而PEPSu 50/50的層狀厚度為2.5 nm。從PBMPSu 50/50 SALS的Hv模式結果只能觀察到隨著結晶時間的增加其強度有增強趨勢,沒有觀察到四葉形的圖案顯現,而PBPSu 50/50 SALS的Hv模式結果則可觀察到四葉形的圖案。由這些實驗結果推論PBMPSu 50/50的結晶形態為纓狀微束晶體,而PBPSu 50/50則呈現共晶行為。
Abstract
Aliphatic copolyesters of poly(butylene succinate-co-50 mol% 2-methyl-1,3- propylene succinate) (PBMPSu 50/50), poly(butylene succinate-co-50 mol% propylene succinate) (PBPSu 50/50), poly(butylene succinate-co-50 mol% ethylene succinate) (PBESu 50/50) and poly(ethylene succinate-co-50 mol% propylene succinate) (PEPSu 50/50) were synthesized through a direct polycondensation reaction with titanium tetraisopropoxide as the catalyst. Their randomness parameters are ~1.00 and average-number sequence lengths are 2.0±0.1, which were calculated from 13C NMR spectra. And their degree of crystallinity is below 20% from analysis of differential scanning calorimeter (DSC). The morphology was studied by using the polarized light microscope (PLM), transmission electron microscope (TEM) and atomic force microscope (AFM). The results of PLM indicate that the PBMPSu 50/50 and PBESu 50/50 displayed granular texture of small and irregular crystals with less birefringence, and the PBPSu 50/50 were displayed the morphology of small spherulites. PEPSu 50/50 revealed the morphology of spherulites with negative birefringence. The PBMPSu 50/50 was displayed the morphology of granule-like and PBPSu 50/50 displays the morphology of short and slightly thinner lamellae by TEM. Study the microstructure of copolymers by using the small angle X-ray scattering (SAXS) and small angle light scattering (SALS). The results of SAXS one dimensional (1-D) correlation function, can obtained the γ(x) only show the first maximum of PBMPSu 50/50 and PBESu 50/50, this fact indicates that the crystal structure exhibits a short range order. The lamellae thickness is about 2.3 nm of PBPSu 50/50 and 2.5 nm of PEPSu 50/50 from analysis of 1-D correlation function. The results of PBMPSu 50/50 SALS, only observed the intensities increases as crystallization time increases, can’t found the four leaves from Hv patterns. And the results of PBPSu 50/50 SALS, can be find the four leaves from Hv patterns. Propose the fringed-micelle-like crystals are developed in the PBMPSu 50/50. And suggest the cocrystallization behavior of PBPSu 50/50.
目次 Table of Contents
誌謝............................................................................................................i
摘要...........................................................................................................ii
Abstract…………………………………………………………………....................iii
Contents…………………………………………………………………………..........v
List of figures……………………………………………………………..................viii
List of tables……………………………………………………………………........xiii
Chapter 1 Introduction………………………………………………………………....1
Chapter 2 Literature review and theoretical background...................................4
2.1 Morphology of fringed micelle………………………....................................4
2.2 Cocrystallization behavior of copolymer………………………………............6
2.3 Theory of copolymer crystallization……………………………………...........8
2.3.1 Flory's Theory of Copolymer Crystallization………..............................9
2.3.2 Sanchez and Eby's Model of Copolymer Crystallization …..................9
2.4 Crystal structure of polyester…………………………………………............11
2.4.1 Poly(butylene succinate) (PBSu)………………………………..............11
2.4.2 Poly(ethylene succinate) (PESu)………………………………..............12
Chapter 3 Experimental...............................................................................15
3.1 Materials.............................................................................................15
3.2 Sample preparation..............................................................................18
3.2.1 Purification.....................................................................................18
3.2.2 Preparation of film by hot press........................................................18
3.3 Instruments..........................................................................................18
3.4 Measurements and Analysis..................................................................20
3.4.1 Wide-angle X-ray diffraction…………………………..............................20
3.4.2 Isothermal crystallization and melting behavior……….........................20
3.4.3 Crystal morphology and microstructure.............................................21
3.4.3.1 Polarized Light Microscopy…………….......................................21
3.4.3.2 Transmission Electron Microscopy……......................................21
3.4.3.3 Atomic Force Microscopy…………….........................................23
3.4.3.4 Small Angle X-ray Scattering………...........................................24
3.4.3.5 Small Angle Light Scattering………...........................................24
Chapter 4 Results and discussion (І).............................................................25
PBMPSu 50/50
4.1 Analysis of wide-angle X-ray diffraction……………...................................25
4.2 Isothermal crystallization and melting behavior………..............................26
4.3 Crystal morphology of PBMPSu 50/50…................................................30
4.4 Microstructure of PBMPSu 50/50….......................................................33
4.5 Model of PBMPSu 50/50…...................................................................40
4.6 Summary.………………………..............................................................43
Chapter 5 Results and discussion (ІІ)...........................................................44
PBPSu 50/50
5.1 Analysis of wide-angle X-ray diffraction…...............................................44
5.2 Isothermal crystallization and melting behavior…....................................45
5.3 Crystal morphology of PBPSu 50/50……...............................................50
5.4 Microstructure of PBPSu 50/50……………………………………...............54
5.5 Model of PBPSu 50/50….....................................................................61
5.6 Summary.……………………….............................................................62
Chapter 6 Results and discussion (ІІІ)..........................................................63
PBESu 50/50 and PEPSu 50/50
6.1 Analysis of wide-angle X-ray diffraction………………………….................63
6.2 Isothermal crystallization and melting behavior……................................65
6.3 Crystal morphology of PBESu 50/50 and PEPSu 50/50…......................70
6.4 Microstructure of PBESu 50/50 and PEPSu 50/50...…………………......72
6.5 Summary.………………………............................................................75
Chapter 7 Conclusion…............................................................................76
References…………………………………………………………………………...78
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