臺灣博碩士論文加值系統

本研究旨在探討苯胺－胺酯共聚物及其與交聯聚胺酯形成的半互穿網狀結構體的氣體透氣行為、微觀結構與物性間的相關性，以期製備具高強度、高通量及高選擇率的分離材料，以應用於富氧氣體與清潔燃料材料的開發。苯胺－胺酯共聚物的合成採二階段方式合成，即以聚醇（含聚酯型與聚醚型）與異氰酸鹽（MDI）合成預聚物，再與適當比例的1,4BD/聚苯胺寡聚合體(oligomer polyaniline,OPA)為鏈延長劑進行聚合而成，半互穿型網狀結構體，則以苯胺－胺酯共聚物與聚胺酯預聚物同時加入鏈延長劑1,4丁二醇（1,4Butanediol,1,4BD）及交聯劑三甲基醇丙烷（Trimethylol propane,TMP）進行聚合反應而成。
苯胺－胺酯共聚物之合成鑑定藉由紅外線光譜儀（FTIR）特性吸收峰及13C NMR鑑定，苯胺－胺酯共聚物及其聚胺酯半互穿型網狀結構體之分子相容性藉由掃描微差熱卡計（DSC）、動態機械分析儀(DMA)及穿透式電子顯微鏡（TEM）測試，氣體透氣性由氣體透氣儀測試，微結構的分析則以原子立場顯微鏡（AFM）觀測其表面微結構，機械性質則以萬能拉力機測試之。
實驗結果顯示，PBA100系列之苯胺-胺酯共聚物及其聚胺酯半互穿型網狀高分子結構體隨著OPA（Oligomer）含量增加其PU軟鏈節的Tg點向高溫方向移動的現象，表示其具較佳的相容性；然而，PTMO 1000系列之苯胺-胺酯共聚物PU軟鏈節的Tg點，隨OPA含量的增加往低溫移動，此為軟區域（soft domain）純化現象（purification）所致。氣體透氣性分析顯示，苯胺-胺酯共聚物及其聚胺酯半互穿型網狀結構體之氣體透氣量隨著OPA含量增加而降低，而其混合氣體的選擇率（CO2/CH4及O2/N2）則隨OPA含量的增加而增加；苯胺-胺酯共聚物/聚胺酯半互穿型網狀結構體之氣體透氣量則隨交聯聚胺酯含量的增加而下降，而其混合氣體的選擇率（CO2/CH4）則隨交聯聚胺酯含量的增加而增加。由熱分析（DMA）存在兩個Tg及TEM存在兩相結構，苯胺-胺酯共聚物為具微相相分離的型態學，而共聚物與半互穿型網狀結構體表面平均粗糙度隨OPA含量的增加而增加。

Abstract
This study concerned about the relationships between gas permeation behavior and microstructure, physical properties of aniline- urethane copolymer and semi-interpenetrating polymer network（Semi-IPNs）.The semi-IPNs was composed of aniline-urethane copolymer and crosslinked polyurethane for the memberanes to own high flux, high selectivity and high strength applied in the development of oxygen-rich and purified fuel gas materials . A series of aniline-containing polyurethane copolymers were synthesized by urethane prepolymer, polyol, 4-4’ diphenylmethane dissocyanate, 1,4butanediol and amine-terminated aniline oligomer as the chain extender . The networks in the semi-interpenetrating polymer network was prepared with aniline-urethane copolymer, PU prepolymer, trimethylol propane and 1,4 butanediol.
The urethane and aniline containing urea of the copolymer had been characterized by Fourier -transform infraed spectroscopy（FTIR）and solid —state NMR spectrometer（13C NMR）. The compatibility of copolymers in Semi -IPNs was also investigated by differential scanning electron calorimeter（DSC, dynamic mechanical analysis（DMA）and transmission electron microscopy（TEM）. The gas permeability properties of Semi-IPNs have been measured by permeation analyzer. The surface microstructure, was detected by atomic force microscopy（AFM）. The mechanical properties were performed by tensilon machine.
From the DSC and DMA thermograns we know the glass transition temperature（Tg）raises with the amount of aniline in the copolymer of type of PBA1000 in that aniline copolymer base on between aniline and urethane block PBA1000 type has a better miscibility. Tg decreases with the content of type of PTMO1000 due to the purification effect from the soft domain in PU. The gas permeation analysis results show the permeability of membranes decreased with amount of polyaniline in copolymer and Semi-IPNs. The gas selectivities increased with amount of polyaniline, due to the incorporation of amine group in PU owning better gas separation . The copolymer and Semi-IPNs have two Tg in the thermal analysis（DMA）and two phase microphase separation in TEM are obsvered .

目 錄
中文摘要 i
英文摘要 ii
目錄 iv
表目錄 vi
圖目錄 vii
第一章、緒論 1
第二章、文獻回顧
2-1 聚胺酯 4
2-2聚苯胺 6
2-3互穿型高分子網狀結構體 9
2-4氣體分離理論 11
第三章、實驗方法
3-1實驗藥品 14
3-2使用儀器 16
3-3實驗流程 17
3-3-1苯胺寡聚合體之合成 17
3-3-2聚胺酯預聚物及聚胺酯之合成 18
3-3-3苯胺-胺酯共聚物的合成 19
3-3-4苯胺-胺酯共聚物/聚胺酯半互穿型高分子網狀
結構體之合成 20
3-4實驗步驟 21
3-4-1苯胺-胺酯共聚體的合成 21
3-4-1-1聚胺酯預聚物之合成 21
3-4-1-2苯胺寡聚合體之合成 21
3-4-1-3聚胺酯之合成 21
3-4-1-4苯胺-胺酯共聚物的合成 21
3-4-1-5苯胺-胺酯共聚物之鑄膜 21
3-4-2苯胺-胺酯共聚物/聚胺酯半互穿型高分子網狀
結構體之合成 21
3-5性質測試 22
第四章、結果與討論
4-1合成物合成鑑定 24
4-1-1FTIR鑑定 24
4-1-2 13C NMR分析 24
4-2 苯胺-胺酯共聚物之物性分析 25
4-2-1微差掃描熱分析（DSC） 25
4-2-2動態機械性質分析（DMA） 26
4-2-3苯胺-胺酯共聚物之機械強度分析 26
4-2-4氣體透氣性之分析 26
4-2-5苯胺-胺酯共聚物之分子作用利 27
4-3苯胺-胺酯共聚物/聚胺酯半互穿型高分子網狀結構體
物性分析
4-3-1苯胺-胺酯共聚物/聚胺酯半互穿型高分子網狀
結構體之機械性質分析 27
4-3-2微差掃描熱分析（DSC） 28
4-3-3動態機械性質分析（DMA） 28
4-3-4氣體透氣性之分析 28
4-4微結構分析
4-4-1掃描式電子顯微鏡（SEM）穿透式電子顯微鏡（TEM）
28
4-4-2原子立場顯微鏡（AFM） 29
第五章、結論 30
第六章、參考資料 31

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