博碩士論文 91324004 詳細資訊




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姓名 賴君偉(Jun-Wei Lai)  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 非極性式poly-ip based PU軟質段末端改質的影響
(The effect of modified end group of poly-ip on properties of PU)
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摘要(中) 嵌段式聚氨基甲酸酯(Segment polyurethane, PU)龐大的化學結構數目以及內部特殊型態的微相結構,反映出多變的性質。本實驗室先前在第二吸熱熔融峰(T2)上之研究,了解到兩相之界面鬆弛,足以構成硬質鏈段在其硬質相域內呈現更規則之排列。而由過去機械性質實驗,亦證明這才是構成極性式PU有極佳機械性質主因。
本實驗將非極性軟段poly-ip進行改質,末端接上不同數量lactone極性單體,以此為新polyol, MDI二異氰酸鹽(4,4-diphenylmethane diisocyanate)及BD鏈延劑(1,4-butadiol extender)為硬質段,利用Two-step溶液聚合法,合成出一系列線性嵌段式共聚物PU。探討其軟段末端改質接上不同極性單體的影響,其末端極性化後,對於界面鬆弛型態結構及動態機械性質有何差別。
由FTIR及NMR結果可證明lacotone有開環並接在Poly-ip軟段末端;此外,一系列軟段末端改質之PU在IR 、DSC之Tg與△B與DMA結果發現,依然是相分離程度很高的系統。而從高溫DSC也可看出軟段末端改質之PU,有非結晶性硬質段排序之T2出現,且看出DSC在melt-quenched後,軟段末端改質之PU在高硬段含量下,有較高硬段Tg及較大結晶峰面積出現,但軟段末端以8個lactone改質之PU之Tg及結晶峰面積又變弱,乃因相分離速率關係,長硬質
鏈段需更多時間才能相分離完全所致;另外,從XRD仍看不出軟段末端改質之PU有結晶出現,DMA方面則看出軟段末端以越多數目lactone改質之PU,在tanδ高溫區peak越往高溫位置移動,表示長硬質鏈段排列越多。但從DSC中T2變化對照,發現長硬質鏈段要排的緊密,才有助於T2位置提昇。而在機械性質方面,除了軟段末端以4個lactone改質之PU 外,軟段末端改質之PU比未改質PU來的好,但提昇有限,乃因除了界面互容之鬆弛有幫助提昇機械性質,但軟質鏈段變長,亦會降低機械性質,但在彼此消長下,機械性質仍是有所提昇。
關鍵字(中) ★ 聚氨基甲酸酯
★ 己內酯
關鍵字(英) ★ caprolactone
★ PU
論文目次 摘要
目錄 -------------------------------------------------------------------------Ⅰ
圖目錄 ----------------------------------------------------------------------Ⅴ
表目錄 ----------------------------------------------------------------------Ⅸ
第一章 序論 --------------------------------------------------------------- 1
第二章 文獻回顧 ----------------------------------------------------------3
2-1 PU之原料 --------------------------------------------------------------4
2-1-1異氰酸鹽 -------------------------------------------------------------5
2-1-2 多元醇(polyol)-----------------------------------------------------7
2-1-3鏈延劑 (Chain extender) ------------------------------------------8
2-1-4 催化劑(Catalyst) ----------------------------------------------------9
2-2PU的熱性質 -----------------------------------------------------------10
2-2-1軟質相的玻璃轉移現像 ------------------------------------------10
2-2-2硬質相的玻璃轉移現象 ------------------------------------------11
2-2-3 硬質相的規則度 --------------------------------------------------12
2-3PU的機械性質 --------------------------------------------------------15
2-3-1軟質段的長度 ------------------------------------------------------15
2-3-2 界面結構與形態 --------------------------------------------------16
2-3-3PU聚合的方法 -----------------------------------------------------17
第三章 實驗
3-1化學藥品 --------------------------------------------------------------19
3-2儀器設備 --------------------------------------------------------------20
3-3實驗步驟 --------------------------------------------------------------21
3-3-1poly-ip軟段改質合成 ---------------------------------------------21
一、ε-caprolactone來改質軟段合成方法 ---------------------------21
二、鑑定 ------------------------------------------------------------------22
Ⅰ.羥基末端分子量的滴定 ---------------------------------------------22
Ⅱ.IR ------------------------------------------------------------------------24
Ⅲ.NMR --------------------------------------------------------------------24
3-3-2PU的合成 ----------------------------------------------------------24
一、反應物 ---------------------------------------------------------------24
二、Poly-ip based PU合成步驟 --------------------------------------24
三、PU試片的製造 -----------------------------------------------------25
四、NCO官能基濃度滴定 --------------------------------------------26
3-4實驗分析方法 --------------------------------------------------------27
3-4-1DSC熱性質分析 ------------------ --------------------------------27
3-4-2動態機械分析(DMA) --------------------------------------------28
3-4-3紅外線光譜分析(FTIR) ------------------------------------------28
3-4-5X光繞射分析(XRD) ----------------------------------------------28
3-4-6拉伸機械性質分析 -----------------------------------------------28
第四章 結果與討論 --------------------------------------------------------30
4-1 以ε-Caprolactone改質Poly-ip之軟段鑑定 ----------------------30
4-1-1 末端羥基分子量滴定法結果 --------------------------------------30
4-1-2 IR鑑定 -----------------------------------------------------------------30
4-1-3 NMR鑑定 --------------------------------------------------------------31
4-2 PU的測試與分析 --------------------------------------------------------32
4-2-1 PU外觀 -----------------------------------------------------------------32
4-2-2 FTIR鑑定 --------------------------------------------------------------33
4-2-3 DSC鑑定 ---------------------------------------------------------------35
4-3-2-1低溫軟質段轉變溫度( Tg ) ---------------------------------------36
4-3-2-2玻璃轉變寬度( △B ) ----------------------------------------------37
4-3-2-3玻璃轉變溫度的比熱( △Cp ) -----------------------------------38
4-3-2-4高溫DSC ------------------------------------------------------------41
4-2-4 XRD( 廣角x-ray ) ---------------------------------------------------44
4-2-5 動態機械性質(DMA) ---------------------------------------------45
4-2-6 機械性質分析 ------------------------------------------------------48
第五章 結論 ----------------------------------------------------------------51
參考文獻 --------------------------------------------------------------------89
圖目錄
圖2.1 線性嵌段式共PU示意圖 ------------------------------------------3
圖3.1 ε-Caprolactone-modified Poly-ip --------------------------------21
圖4-1 純ε-Caprolactone單體IR圖譜 ----------------------------------60
圖4-2 未改質純Poly-ip及接不同程度單體ε-Caprolactone之
Poly-ip IR圖譜 ----------------------------------------------------61
圖4-3(a) 純Poly-ip之NMR圖譜 ---------------------------------------62
圖4-3(b) 接2個lactone的Poly-ip之NMR圖譜 --------------------62
圖4-3(c) 接4個lactone的Poly-ip之NMR圖譜 --------------------63
圖4-3(d) 接8個lactone的Poly-ip之NMR圖譜 -------------------63
圖4-4未改質之Poly-ip based PU之IR圖譜,圖中(a)、(b)、(c)分別依序硬質段含量35、45、55% ---------------------------------64
圖4-5-1 硬質段含量為35%的PU IR圖譜,圖中(a)、(b)、(c)、(d)依
序為沒改質Poly-ip 、接2、4、8 lactone Poly-ip之PU
-------------------------------------------------------------------------65
圖4-5-2 硬質段含量為45%的PU IR圖譜,圖中(a)、(b)、(c)、(d)依
序為沒改質Poly-ip 、接2、4、8 lactone Poly-ip之PU
-------------------------------------------------------------------------66
圖4-5-3 硬質段含量為55%的PU IR圖譜,圖中(a)、(b)、(c)、(d)依
序為沒改質Poly-ip 、接2、4、8 lactone Poly-ip之PU
-------------------------------------------------------------------------67
圖4-6-1 PU-0-yy系列sample的高溫DSC 1st圖譜,硬質段含量yy
,yy=35、45、55% ----------------------------------------------68
圖4-6-2 PU-2-yy系列sample的高溫DSC 1st圖譜,硬質段含量yy
,yy=35、45、55% ----------------------------------------------69
圖4-6-3 PU-4-yy系列sample的高溫DSC 1st圖譜,硬質段含量yy
,yy=35、45、55% ----------------------------------------------70
圖4-6-4 PU-8-yy系列sample的高溫DSC 1st圖譜,硬質段含量yy
,yy=35、45、55% ----------------------------------------------71
圖4-6-5 PU-x-55系列sample的高溫DSC 1st圖譜,x= lactone改質末
端軟段含量(0、2、4、8) ----------------------------------------72
圖4-7-1 Melt-quenched PU-0-yy系列sample的高溫DSC 2nd圖譜, 硬
質段含量yy,yy=35、45、55% ------------------------------73
圖4-7-2 Melt-quenched PU-2-yy系列sample的高溫DSC 2nd圖譜, 硬
質段含量yy,yy=35、45、55% ------------------------------74
圖4-7-3 Melt-quenched PU-4-yy系列sample的高溫DSC 2nd圖譜, 硬
質段含量yy,yy=35、45、55% ------------------------------75
圖4-7-4 Melt-quenched PU-8-yy系列sample的高溫DSC 2nd圖譜, 硬
質段含量yy,yy=35、45、55% ------------------------------76
圖4-8-1 PU-0-yy系列sample的XRD光譜圖,硬質段含量yy, yy=35、45、55% -----------------------------------------------77
圖4-8-2 PU-2-yy系列sample的XRD光譜圖,硬質段含量yy,
yy=35、 45、55% ---------------------------------------------78
圖4-8-3 PU-4-yy系列sample的XRD光譜圖,硬質段含量yy,
yy=35、 45、55% ---------------------------------------------79
圖4-8-4 PU-8-yy系列sample的XRD光譜圖,硬質段含量yy,
yy=35、 45、55% ---------------------------------------------80
圖4-9-1 PU-0-yy系列sample之DMA圖譜,硬質段含量yy,yy
=35、45、55% --------------------------------------------------81
圖4-9-2 PU-2-yy系列sample之DMA圖譜,硬質段含量yy,yy
=35、45、55% --------------------------------------------------82
圖4-9-3 PU-4-yy系列sample之DMA圖譜,硬質段含量yy,yy
=35、45、55% --------------------------------------------------83
圖4-9-4 PU-8-yy系列sample之DMA圖譜,硬質段含量yy,yy
=35、45、55% --------------------------------------------------84
圖4-9-5 相同硬質段含量35%PU sample之DMA圖譜 ----------85
圖4-9-6 相同硬質段含量45%PU sample之DMA圖譜 ----------86
圖4-9-7 相同硬質段含量55%PU sample之DMA圖譜 ----------87
圖4-10 Stress-strain of PU-x-yy,lactone改質末端軟段含量x= 0、2、
4、8,硬質段含量y=35、45、55% -------------------------88
表目錄
表4-1 軟段末端羥基分子量 --------------------------------------------30
表4-2 Poly-ip and Poly-ip modified with lactone based PU的熱轉變數據,玻璃轉換溫度Tg,玻璃轉換寬度△B和玻璃轉換比熱△Cp --------------------------------------------------------------------54
表4-3 Melt-quenced Poly-ip and Poly-ip modified with lactone based PU的熱轉變數據 -------------------------------------------------------55
表4-4 高溫DSC 2nd run圖譜,Tgh與放熱、吸熱峰之溫度及△H -----------------------------------------------------------------------56
表4-5 PU DMA 測試下,在tanδ中觀察到高溫區α peak及低溫區β peak ------------------------------------------------------------------57
表4-6 PU硬質段的分子量及多少MDI-BD重覆單位 -------------58
表4-7 PU-x-yy系列之機械性質 ----------------------------------------59
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指導教授 陳登科(T. K. Chen) 審核日期 2004-7-14
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