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中文論文名稱 非異氰酸酯製程含聚二甲基矽氧烷之水性聚胺酯研究與探討
英文論文名稱 Preparations of Polydimethylsiloxane containing Aqueous-based PU via a Non-isocyanate Process
校院名稱 淡江大學
系所名稱(中) 化學學系碩士班
系所名稱(英) Department of Chemistry
學年度 97
學期 2
出版年 98
研究生中文姓名 林忠政
研究生英文姓名 Jhong-Jheng Lin
電子信箱 royroyroy0001@hotmail.com
學號 696160356
學位類別 碩士
語文別 中文
口試日期 2009-07-19
論文頁數 92頁
口試委員 指導教授-陳幹男
委員-葉正濤
委員-王權泉
中文關鍵字 環氧樹脂  水性聚胺酯  聚二甲基矽氧烷 
英文關鍵字 Epoxy  PDMS  aqueous-based  polyurethane 
學科別分類 學科別自然科學化學
中文摘要 以環氧樹脂(DGEBA)在常壓下通入二氧化碳進行親核開環反應得到環狀碳酸酯Bis(cyclic carbonate),再以具有聚二甲基矽氧烷(PDMS)的胺類化合物進行聚合反應,使形成主鏈段上掛有羥基的聚胺基甲酸酯(Hydroxyl PU)。再利用PU上的羥基與琥珀酸酐(Maleic anhydride)進行半酯化反應後,使其PU鏈段懸掛羧酸基,因而此新型水性PU樹脂能夠穩定分散於水中,即所謂水性PU分散液(Aqueous-based Polyurethane Dispersion)。最後使用架橋劑(TMPTA-AZ)使水性PU樹脂成為網狀交聯之結構,測量並討論其物理與熱性質。
英文摘要 Bis(cyclic carbonate) were prepared from the DGEBA reacted in the atmospheric pressure of CO2 . And then, use the polydimethy siloxane(PDMS) which included the amino group to afforded corresponding poly(hydroxyurethane)s. Half-esterification between these pendent hydroxyl groups and maleic anhydride could lead to new pendent groups, carboxylic groups. The carboxylic group could play the role of internal emulsifier that could dispersed steadily in the water, named aqueous-based polyurethane dispersion. Adding different ratio of bridging agent TMPTA-AZ(trimethylolpropane triacrylate-aziridine) into the WPU dispersion, would lead to cure by cross-linking. We discussed the properties of physics, thermal stability, dynamic mechanics in this research.
論文目次 中摘
英摘
一、前言………………………………………………………………1

二、實驗…………………………………………………………………39
2-1 藥品……………………………………………………………39
2-2 儀器……………………………………………………………40
2-3實驗步驟……………………………………………………………41
2-3-1 Bis (cyclic carbonate)s 合成步驟………………………41
2-3-2羥基側鏈懸掛型聚胺酯 (Hydroxyl-PU) 的製備..……………41
2-3-3 羧酸基側鏈掛型聚胺酯 (Carboxylic-PU)的製備……………42
2-3-4 羧酸基側鏈懸掛水性聚胺酯 (Aqueous-Based Carboxylic PU)43
2-4 膠體層析法(GPC) …………………………………….…………44
2-5 物理性質測試……………………………………….……………45
2-6 薄膜熱性質測試……………………………………………..……48
2-7 光譜鑑定……………………………………………………..……50
2-8改善反應條件………………………………………………………51
2-9 以三官能基五雜環當架橋劑…………………………………..…52
2-9-1 Tri (cyclic carbonate)s 合成步驟…………………………52
2-9-2 加入不同比例Tri (cyclic carbonate)s……………………52

三、結 果 與 討 論……………………………………………………53
3-1本實驗研究討論方向………………………………………………53
【Part A】 PDMS-diamine 系列
3-2A光譜分析…………………………………………….……………55
3-2A-1 Bis (cyclic carbonates)s的光譜分析……………………55
3-2A-2 PDMS-diamine系列各比例羥基側鏈懸掛型PU(Hydroxyl-PU)的光譜分析……………………………………………………..………58
3-2A-3 PDMS-diamine系列各比例羧酸基側鏈懸掛型PU (Carboxylic- PU) 光譜分析……………………………………………………….…59
3-3A物理性質分析…………………………………………….………60
3-3A-1膠含量(Gel Content)………………………………………61
3-3A-2吸水率(Water-Uptake, WA%)及對水損失率(Weight loss in water, WL%)………………………………………………………62
3-3A-3 吸乙醇率(Ethanol-Uptake, EA%)及對乙醇損失率(Weight loss in ethanol, EL%)…………………………………64
3-4A熱性質分析………………………………………………….……65
3-4A-1熱重分析(Thermalgravity Analysis, TGA)………………65
3-5A機械性質……………………………………………………….…70
3-5A-1動態機械分析(Dynamic Mechanical Analysis, DMA)....70
【Part B】改善反應條件所得分子量
3-2B 以GPC分析各項分子量……………………………………...…75
3-2B-1在不同時間下的微波反應…………………………………..…76
3-2B-2不同功率下的微波反應…………………………………..……77
【Part C】以三官能基五雜環當架橋劑各項性質
3-2C光譜分析 FT-IR (Fourier Transform – Infrared Rays) …78
3-3C物理性質分析……………………………………………………..80
3-3C-1膠含量(Gel Content)………………………………………80
3-3C-2吸水率(Water-Uptake, WA%)及對水損失率(Weight loss in water, WL%)………………………………………………………81
3-3C-3 吸乙醇率(Ethanol-Uptake, EA%)及對乙醇損失率(Weight loss in ethanol, EL%)…………………………………81
3-4C 熱性質分析………………………………………………………82
3-4C-1熱重分析(Thermalgravity Analysis, TGA)………………83
3-5C 機械性質…………………………………………………………85
3-5C-1動態機械分析(Dynamic Mechanical Analysis, DMA)……85

四、結論…………………………………………………………….…87
五、參考資料……………………………………………………….….89

圖 表 目 錄
圖3.1A DGEBA的H1-NMR光譜……………………………………...56
圖3.2A Bis (cyclic carbonate)s 的H1-NMR光譜……………………...56
圖3.3A 2,2-Bis (4-glycidyloxypheyl) propane (DGEBA)的FT-IR光譜57
圖3.4A Bis (cyclic carbonate)s 的FT-IR光譜…………………………58
圖3.5A PDMS-diamine系列各比例羥基側鏈懸掛型PU FT-IR光譜...59
圖3.6A PDMS-diamine系列各比例羧酸基側鏈懸掛型PU FT-IR…...60
圖3.7A PDMS-diamine系列(Car.:amine=1.0:0.8)水性PU數脂與各比例TMPTA-AZ架橋反應薄膜於氮氣系統之TGA圖…………….66
圖3.8A PDMS-diamine系列(Car.:amine=1.0:0.8)水性PU數脂與各比例TMPTA- AZ架橋反應薄膜於氮氣系統之TGA一次微分圖....66
圖3.9A PDMS-diamine系列(Car.:amine=1.0:1.0)水性PU數脂與各比例TMPTA- AZ架橋反應薄膜於氮氣系統之TGA圖……………67
圖3.10A PDMS-diamine系列(Car.:amine=1.0:1.0)水性PU數脂與各比例TMPTA-AZ架橋反應薄膜於氮氣系統TGA一次微分圖..67
圖3.11A PDMS-diamine系列(Car.:amine=1.0:1.1)水性PU數脂各比例TMPTA- AZ架橋反應薄膜於氮氣系統之TGA圖………..…68
圖3.12A PDMS-diamine系列(Car.:amine=1.0:1.1)水性PU數脂各比例TMPTA- AZ架橋反應薄膜於氮氣系統TGA一次微分圖......68
圖3.13A PDMS-diamine系列(Car.:amine=1.0:0.8)水性PU數脂各比例TMPTA- AZ架橋反應薄膜之DMA圖……………………….70
圖3.14A PDMS-diamine系列(Car.:amine=1.0:0.8)水性PU數脂各比例TMPTA- AZ架橋反應薄膜tanδ對溫度之DMA圖……….…71
圖3.15A PDMS-diamine系列(Car.:amine=1.0:1.0)水性PU數脂與各比例TMPTA-AZ架橋反應薄膜之DMA圖………………….…71
圖3.16A PDMS-diamine系列(Car.:amine=1.0:1.0)水性PU數脂各比例TMPTA- AZ架橋反應薄膜tanδ對溫度之DMA圖…….……72
圖3.17A PDMS-diamine系列(Car.:amine=1.0:1.1)水性PU數脂各比例TMPTA- AZ架橋反應薄膜之DMA圖…………………….…72
圖3.18A PDMS-diamine系列(Car.:amine=1.0:1.1)水性PU數脂各比例TMPTA- AZ架橋反應薄膜tanδ對溫度之DMA圖……….…73
圖3.1B微波反應不同時間下之分子量作圖……………………….…73
圖3.2B不同功率下一樣的時間所得分子量作圖…………………….78
圖3.1C Trimethylolpropane Triglycidyl Ether之FT-IR光譜……79
圖3.2C Tri(cyclic carbonate)s之FT-IR光譜………………………79
圖3.3C以不同比例三官能基五雜環當架橋劑成膜後薄膜於氮氣系統之TGA圖 ……………………………………………83
圖3.4C以不同比例三官能基五雜環當架橋劑成膜後薄膜於氮氣系統之TGA一次微分圖………………………………………...…83
圖3.5C以不同比例三官能基五雜環當架橋劑成薄膜之DMA圖…...85
圖3.6C以不同比例三官能基五雜環當架橋劑成膜後薄膜之tanδ對溫度之DMA圖………………………………………………..…85

Table 3.1A PDMS-diamine系列水性PU薄膜之物理性質……………61
Table 3.2A PDMS系列PU薄膜之熱裂解溫度與玻璃轉移溫度(Tg) .65
Table 3.1B 不同反應條件下所偵測分子量…………………………75
Table 3.2B 微波反應不同時間下之分子量…………………………76
Table 3.3B 不同功率下一樣的時間所得分子量………………….…77
Table 3.1C PDMS-diamine系列水性PU薄膜之物理性質……………80
Table 3.2C三官能基五雜環當架橋劑成膜之熱裂解溫度與玻璃轉移溫度(Tg) ……………………………………………………….…82
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