博碩士論文 953204011 詳細資訊




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姓名 王啟蒼(Chi-Tsang Wang)  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 巨大基團的合成及巨大基團對Polyurethane urea 結構與性質的影響
(Bulky groups synthesis and structure-property effect of bulky group to polyurethane urea )
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摘要(中) 嵌段式聚氨基甲酸酯(Segmented Polyurethane,SPU)是由軟質段與硬質段交替相連之的-(HS)n-型多團聯嵌段式共聚合物。PU因軟、硬質段可選擇之結構種類多,所擁有的化學結構種類相當多,加上其內部特殊的微相型態,反應出相當多變的性質;但也因此使得PU的型態、結構與性質間的關係複雜化。因此,我們藉由合成完全相分離的PU來探討此微區型態及型態變化的關係。
本實驗室過去曾探討自行合成的水性PU(Waterbone Polyurethane,WPU)型態及結構,在結構變化與物性間的關係有重要發現,搭配用穿透式電子顯微鏡對於微相結構的觀察結果,建立了三個水性PU的模式;而此水性PU特有之雙連續相網狀結構(Phase separated bicontinuous network structure)也使此種水性PU具有高透明性、高拉伸剛性、高堅韌性、耐高溫且易加工等特性。本研究將原本水性PU具水溶性的離子基部份改質為不具水溶性的基團,利用兩階段溶液聚合法合成非離子型PU,希望維持其材料特性並期望能將此高分子實用化。
本研究自行合成兩種醯胺-雙醇類作為取代水性PU離子基(DMPA)的巨大基團(Bulky group),搭配FT-IR、H-NMR及MS進行結構鑑定。而後將以兩階段溶液聚合法分別導入此兩種巨大基團進行硬質段部份的改質,由不同巨大基團添加量與不同硬質段含量,再搭配FT-IR、DSC、DMA及拉力機的分析,探討巨大基團對PUU結構與性質的影響。
摘要(英) A series of nonpolar segmented polyurethaneurea(PUU) with bulky side group have been synthesized and their structure-property relationship have been investigated. The bulky group is a molecule that can make a space about 1nm beside the backbone to interfere the hard segment domain. The PUU based on 4,4’-dicyclohexylmethane diisocyanate (H12MDI), polyisoprene(Poly-IP,MW 2500),ethylenediamine(EDA) and two kinds of bulky groups are synthesized by two-step solution polymerization. Hard-segment content (35,45,55,70 wt%) and bulky group contents (0,4.5,8,10,15 wt%) are varied and their effect on the properties are studied. Properties are studied by Fourier-Transform Infrared(FT-IR),Differential Scanning Calorimetry(DSC),Dynamic Mechanical Analysis(DMA) and tensile-strain testing.
The bulky groups (I and II) are two kinds of self-synthesized amide-diol that are reacted by trimethylacetic acid(TMAA) and dipropylacetic acid (DPAA) separately with 2-Amino-2-methyl-1,3-propanediol(AMPD). Chemical structures of bulky groups are characterized by FT-IR, Nuclear Magnetic Resonance(NMR) and Mass Spectroscopy (MS).The yields of bulky I and II are about 42.5% and 40.7%.
The introduction of bulky group result in the C=O stretching of urea and urethane both shift to higher wavenumbers means that the hydrogen bonding strength is reduced. The storage modulus, Young’s modulus and tensile strength are increasing with increasing hard-segment content, but elongation at break is decreasing on the contrary. As the bulky group exists in PUU, the hard-segment domain may become loosely that is to say intermolecular force (cohesive energy) between hard segments is weakening. So the mechanical properties are reduced including Young’s modulus, tensile strength and elongation at break.
關鍵字(中) ★ 巨大基團
★ 結構與性質
關鍵字(英) ★ PUU
★ bulky
★ structure-property
論文目次 摘要----------------------------------------------------------------------------I
英文摘要----------------------------------------------------------------------II
致謝--------------------------------------------------------------------------------III
目錄-------------------------------------------------------------------------------IV
圖目錄----------------------------------------------------------------------------VI
表目錄----------------------------------------------------------------------------IX
第一章 、緒論 ------------------------------------------------------------------1
第二章 、文獻回顧 ------------------------------------------------------------3
2.1 PU軟、硬質段的結構組成---------------------------------5
2.2 PU的型態與結構- -- - -- - -- - -- -- - -- - -- - -- - -- - - -- - -- - -- - --11
2.3 水性PU 的型態與結構--------------------------------------15
第三章 、實驗部份-------------------------------------------------------18
3.1 研究流程 ------------------------------------------------------18
3.2 系統設計 --------------------------------------------------------18
3.3 藥品 --------------------------------------------------------19
3.4 實驗流程 ----------------------------------------------------------20
3.4.1 Bulky group 合成--------------------------------------------20
3.4.2 PUU 合成--------------------------------------------------21
3.4.3 實驗樣品命名-----------------------------------------------22
3.4.4 PU 試片製備--------------------------------------------23
3.4.5 實驗裝置圖--------------------------------------------24
3.5 分析鑑定--------------------------------------------------------25
3.5.1 紅外光光譜--------------------------------------------25
V
3.5.2 核磁共振光譜--------------------------------------------26
3.5.3 質量光譜------------------------------------------------------28
3.5.4 微差熱掃描分析儀------------------------------------------29
3.5.5 動態機械分析 ----------------------------------------------31
3.5.6 抗張強度測試 ----------------------------------------------31
第四章 、結果與討論----------------------------------------------------------32
4.1 Bulky group合成及鑑定---------------------------------------------32
4.1.1 醯氯化反應----------------------------------------------------32
4.1.2 醯胺化反應----------------------------------------------------37
4.2 Polyurethaneurea(PUU)合成及性質探討-------------------------49
4.2.1 成膜結果-------------------------------------------------------49
4.2.2 FTIR 分析------------------------------------------------------50
4.2.3 DSC熱分析----------------------------------------------------58
4.2.4 DMA(動態機械性質)分析-------------------------------61
4.2.5 機械性質-------------------------------------------------------64
第五章 結論 ---------------------------------------------------------------67
第六章 參考文獻 ------------------------------------------------------------69
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指導教授 陳登科(Teng-Ko Chen) 審核日期 2008-7-20
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