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
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指導教授 蔣孝澈(A.S.T. Chiang) 審核日期 2000-7-12
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